AN ABSTRACT OF THE DISSERTATION OF
Doolalai Sethajintanin for the degree of Doctor of Philosophy in Toxicology presented on
September 2, 2005.
Title: Passive Sampling Devices as Biological Surrogates for Evaluating Seasonal
Bioavailability of Hydrophobic Organic Contaminants in Surface Water.
Redacted for Privacy
Abstract approved
Kim A. Anderson
The seasonal distribution of bioavailable organochiorine contaminants in surface
water and the potential environmental factors influencing their bioavailability were
evaluated. The study was carried at the lower Willamette River at Portland Harbor, Oregon
where surface water runoff varied according to season. Bioavailable water concentrations of
DDTs and PCBs were determined using a polyethylene membrane containing passive
sampling device (PSD), known as semipermeable membrane device (SPMD). Our findings
indicated that the influence of river seasonality on the bioavailable distributions of
organochiorine contaminants was compound- and site-specific. Bioavailable DDTs
concentrations were strongly affected by the local historic use of DDTs and seasonal changes
in river conditions. The dominance of bioavailable p,p'-DDD and large DDD/DDE ratios
observed during low flow condition in summer suggest redistribution of p,p'-DDD into the
water column and conditions favoring reductive dechlorination of p,p'-DDT to p,p'-DDD. In
contrast, bioavailable dieldrin and PCB concentrations were significantly increased during
high flow condition in fall, especially during episodic rainstorm events. While a discernable
seasonal pattern for PCBs was observed along the 18-mile stretch study area, the seasonal
pattern of dieldrin was only apparent at the sampling site downstream of an agricultural creek
with historical use of dieldrin. The increase in bioavailable PCB concentrations and daily
loads cOincident with high precipitation and sewer overflows in fall suggested a significant
contribution of PCBs from precipitation input and urban storm water discharges to the
surface water. Seasonal bioavailable concentrations of organochiorine compounds exceeded
the national and the Oregon water quality criteria revealing the significance of considering
realistic seasonal and site-specific influences on bioavailable organochiorine distributions
when performing risk assessments. In addition, we developed the triolein-free polyethylene
lay flat tubing (LFT) as an alternative in situ PSD. The LFT proved reliable and had the same
benefits as SPMD, but was simpler, inexpensive and lacked interference from the triolein
impurities. The LFT tended to accumulate compounds with high log K0 faster than SPMD.
LFT sampling rates were estimated and modeled for 33 target analytes, including PAHs,
PCBs, and organochiorine pesticides. The successful determination of field derived data
illustrates the effectiveness and reliability of LIT for environmental monitoring.
© Copyright by Doolalai Sethajintanin
September 2, 2005
All Rights Reserved
Passive Sampling Devices as Biological Surrogates for
Evaluating Seasonal Bioavailability of
Hydrophobic Organic Contaminants in Surface Water
by
Doolalai Sethajintanin
A DISSERTATION
submitted to
Oregon State University
in partial fulfillment of
the requirements for the
degree of
Doctor of Philosophy
Presented September 2, 2005
Commencement June 2006
Doctor of Philosophy dissertation of Doolalai Sethajintanin presented on September 2, 2005.
APPROVED:
Redacted for Privacy
Major Professor, representing Toxicology
Redacted for Privacy
Head of the Department of Environmental and Molecular Toxicology
Redacted for Privacy
Dean of th-
radiiate School
I understand that my dissertation will become part of the permanent collection of Oregon
State University Libraries. My signature below authorizes release of my dissertation to any
reader upon request.
Redacted for Privacy
Doolalai Sethajintanin, Author
ACKNOWLEDGMENTS
Many people have contributed, in various ways, to this accomplishment, and it is not
feasible in limited space to mention them all. I would like to express my sincere appreciation
to my major professor, Dr. Kim A. Anderson, for providing guidance, encouragement, partial
financial support and many opportunities for regional and national conferences. Her advice
and generosity are appreciated. I acknowledge my graduate committee, Drs. Lawrence R.
Curtis, Jeffrey J. Jenkins, Staci L. Simonich and Daniel D. Rockey, for contributing
suggestions and comments to this study. Special thanks go to Dr. Jennifer A. Field for
reviewing and contributing valuable comments to Chapter 2.
This study was partially funded by the Society of Environmental Toxicology and
Chemistry (SETAC) Early Career for Applied Ecological Research Award sponsored by the
American Chemistry Council awarded to Dr. Kim A. Anderson. The Oregon Department of
Environmental Quality for the McCormick & Baxter superfund site project 2002-2003 and
the Oregon Health Science University pilot project for the NIEHSIEPA Superfund Basic
Research Grant provided partial financial support.
I am deeply indebted to the Royal Thai Government Scholarship for financial
support. The Food and Drug Administration, Ministry of Public Health, Thailand, is
acknowledged for providing me the opportunity to pursue my master and doctor degrees. I
thank all of my teachers for contributing to my knowledge.
I am grateful for field assistance by Robert Grove of Forest and Rangeland
Ecosystem Science Center, Corvallis, Oregon. It is a pleasure to acknowledge the field and
laboratory assistance from my colleagues at the Anderson Lab group; Eugene Johnson,
Bobby Loper, Solyssa Visalli, Gregory Sower, Jennifer Basile, Roger Adams, Angela Perez,
Oraphin Krissanakriangkrai, Lucas Quarles, and Dr. Wendy Hiliwalker. I am especially
grateful to Eugene Johnson and Bobby Loper for their wonderful kindness. Special thanks go
to the Anderson Lab group, all of my friends at Oregon State University, my officemates
(Kimberly Hageman and Junga Lee) and my little Thai community who made my days in
Corvallis memorable. I would like to thank my Thai friends in Thailand and the US,
especially Yuda Chongpison and Arusa Chaovanalikit, for supporting and encouraging me
emotionally.
Last but not least, I would like to thank the most important people in my life, my
mom and dad (Prajoub and Chinta Sethajintanin), for always being there and loving support
although physically thousands of miles away. Without their loves and inspiration this
accomplishment would not have been possible.
CONTRIBUTION OF AUTHORS
This study was conducted with the contributions of the following co-authors. Dr. Kim
A. Anderson provided guidance on all aspects of this dissertation. Eugene R. Johnson
participated in the preparation of triolein-free low density polyethylene membrane in Chapter
3 and the chemical analysis work in Chapter 4.
TABLE OF CONTENTS
Page
CHAPTER 1
INTRODUCTION
1
Background
5
Bioavailability
5
Significance of spatial and seasonal aspects on
chemical distribution
7
Passive sampling technique as surrogate for
evaluating bioavailability
8
Organochiorine compounds in aquatic system
..12
Study area: the lower Willamette River at
Portland Harbor, Oregon
15
Hypotheses and objectives
.17
Literature Cited
18
CHAPTER 2 EVALUATION OF SEASONAL BIOAVAILABILITY
OF ORGANOCHLORINE PESTICIDES AND PCBS AT
A SUPERFUND SITE USING PASSIVE SAMPLING DEVICE
23
Abstract
24
Introduction
25
Materials and Methods
Results and Discussion
..
.28
.33
River conditions and water chemistry
.33
Distributions of bioavailable DDT concentrations and
Potential sources
36
Dominance of bioavailable p, p'-DDD in surface water
TABLE OF CONTENTS (Continued)
Page
Evidence of seasonality in bioavailable DDT concentrations
41
Potential risk of seasonal bioavailable DDTs on aquatic
organisms
45
Distribution of bioavailable polychlorinated biphenyls (PCBs)
48
Seasonal changes in bioavailable PCB distribution
50
Bioavailable PCB composition in surface water
50
PCBs-associated risks to aquatic community and human health
54
Seasonal changes in bioavailable dieldrin distribution
Literature Cited
CHAPTER 3 FIELD TRIAL OF TRIOLEIN-FREE LOW DENSITY
POLYETHYLENE MEMBRANE AS AN IN SITU
PASSIVE WATER SAMPLER
.
.55
57
.63
Abstract
64
Introduction
65
Materials and Methods
68
Results and Discussion
73
Evaluation of the spiking method of permeability/performance
Reference compounds (PRCs) in LFT
73
Demonstration of effectiveness and reliability of LFT for
field deployment
.75
Literature Cited
92
TABLE OF CONTENTS (Continued)
Page
CHAPTER 4 ENVIRONMENTAL STRESSES AND FISH DEFORMITIES
IN THE WILLAMETTE RIVER: COMPARISON OF
PERSISTENT BIOACCUMULATIVE TOXICANTS
.96
Abstract
97
Introduction
98
Materials and Methods
.100
Results and Discussion
.103
Water chemistry characterization
103
Bioavailable polychiorinated biphenyls (PCBs)
.. 106
p, p'-DDT and its metabolites
107
Dieldrin
108
Literature Cited
.109
CHAPTER 5 CONCLUSIONS
..111
BIBLIOGRAPHY
.116
APPENDIX A Estimated river concentrations of bioavailable p,p'-DDT
and its metabolites, dieldrin, and PCBs (sum of 25 congeners)
at the Willamette River during summer and fall of 2001 to 2004.
River concentrations were estimated from SPMD concentrations.
Deployments of SPMDs were typically 7-to 21-days long
126
APPENDIX B Sewer overflow points in Portland area
.. .
.131
APPENDIX C Equations used to estimate molecular diffusivity in water (D)
.. .
.132
APPENDIX D Predicted values for LFT sampling rates using different methods
133
APPENDIX E Environmental stresses and skeletal deformities in fish from
the Willamette River, Oregon
134
LIST OF FIGURES
Figure
Figure 1.1
Figure 1.2
Page
Schematic representation of bioavailability as modified from
Dickson et al. 1994 and Wells and Lanno 2001
5
A simple four-phase model describing the bioavailabiiity and
the partitioning approach to the distribution of organic contaminant
in water-sediment systems
.6
Figure 1.3
Generalized uptake profile for a passive sampling device
10
Figure 1.4
The three compartment model for contaminant accumulation by
SPMD as proposed by Gale 1998
Figure 2.1
Figure 2.2
Figure 2.3
Figure 2.4
Figure 2.6
Figure 2.7
Figure 2.8
..11
The lower Willamette River at Portland, Oregon, showing locations
of the sampling sites (RM = river mile)
.29
Average concentrations of bioavailable DDTs in surface water at
the lower Willamette River at Portland Harbor, Oregon, using passive
sampling device (n=186)
38
Distributions of bioavailable p, p'-DDD: p, p'-DDE ratios in surface
water at the Willamette River, Oregon during the periods of low flow
in summer, and high flow in fall from 2001 to 2004 (n=186)
40
Estimated concentrations of bioavailable p, p'-DDT and its metabolites
in surface water at River Mile 7West of the lower Willamette River at
Portland Harbor, Oregon
42
Spatial and seasonal distribution of bioavailable p, p' -DDT and its
metabolite water concentration estimates compared to the national
recommendation water criteria and Oregon criteria
47
Average concentration estimates of bioavailable PCB (pgIL) in
water at the Willamette River, Oregon according to river season
Average percentage contribution of PCB congeners in surface water
at the lower Willamette River during the periods of low flow in
summer and high flow in fall in 2001 to 2004
.49
51
LIST OF FIGURES (Continued.)
Figure
Figure 2.9
Figure 2.10
Figure 2.11
Figure 3.1
Figure 3.2
Figure 3.3
Figure 3.4
Figure 3.5
Figure 3.6
Page
Average ratios of PCB homolog to bioavailable PCBs (sum of 25
individual PCB congeners) in surface water at the lower Willamette
River
.
..52
Spatial and seasonal distribution of bioavailable PCB water
concentration estimates (sum of 25 individual PCB congeners)
compared to the national recommendation water criteria and Oregon
criteria
55
Seasonal distribution of bioavailable dieldrin in surface water at the
lower Willamette River at Portland Harbor, Oregon during the period
of low flow in summer and high flow in fall of 2001-2004
56
Relationship of contaminant concentrations in the triolein-free
polyethylene lay flat tubing (LIT) and in semipermeable membrane
device (SPMD)
81
Comparison of spatial distributions of selected contaminants
accumulated in the triolein-free polyethylene lay flat tubing and in
semipermeable membrane device (SPMD)
83
Percent comparison of PCBs and PAHs (average ± lsd) in the
triolein-free polyethylene lay flat tubing (LFT) and semipermeable
membrane device (SPMD)
.84
Average ratios of concentration of contaminants accumulated in
the triolein-free polyethylene lay flat tubing (LFT) and in
semipermeable membrane device (SPMD)
84
Sampling rate estimates (RL) of a 540 cm2 triolein-free
polyethylene lay flat tubing (LIT) as a function of log K0, molecular
volume, molar volume, and minimal molecular two-dimension
Sampling rate estimates of a 540 cm2 triolein-free
polyethylene lay flat tubing (LIT) as a function of the product of
aqueous diffusitivity, log K0, and minimal molecular two-dimension
.
88
90
LIST OF FIGURES (Continued.)
Figure
Figure 4.1
Figure 4.2
Page
The Willamette Basin showing the general location and course of the
Willamette River and primary study locations
99
The mean concentration distribution of bioavailable p, p' -DDT,
p, p'-DDD, and p, p'-DDE at Newberg and Corvallis in 2002 and 2003.. ..107
LIST OF TABLES
Table
Table 1.1
Pace
List of target PCBs and organochiorine pesticides and their
physicochemical properties at 20-25 °C
14
Summary of river conditions and water chemistry parameters
at Portland Harbor during SPMD deployment
34
Summary results of total organic carbon (TOC), dissolved
organic carbon (DOC), total suspended solids (TSS), and total
dissolved solids (TDS) at the Willamette River, Oregon during
SPMD deployment
.35
Table 3.1
Selected physicochemical properties of target analytes
.69
Table 3.2
Percent recoveries of permeability/performance reference
compounds using simple spiking method in a small volume of
Table 2.1
Table 2.2
Table 3.3
Table 3.4
toluerie
.74
Percent recoveries and clearance rates of permeability/performance
reference compounds in the field exposed polyethylene lay flat
tubing (LFT) and semipermeable membrane device (SPMD) under
different field condition
78
Contaminant sampling rates for triolein-free polyethylene lay flat
tubing (LFT) estimated from field exposure to contaminated water
at the lower Willamette River at Portland Harbor, Oregon for
2ldays
87
Table 4.1
Spatial and temporal variations of water quality parameters at Newberg
(River Mile 44-47) versus Corvallis (River Mile 135) sampling sites on
the Willamette River, Oregon
.104
Table 4.2
Mean concentrations (pg/L) of bioavailable organochlorines
estimated from concentrations accumulated in semipermeable
membrane devices (SPMDs) exposed for 21 days at the Willamette
River at Newberg and Corvallis (2 sampling sites per location) in
2002 and 2003
.. 106
PASSIVE SAMPLING DEVICES AS BIOLOGICAL SURROGATES
FOR EVALUATING SEASONAL BIOAVAILABILITY OF
HYDROPHOBIC ORGANIC CONTAMINANTS IN SURFACE WATER
CHAPTER 1
INTRODUCTION
Understanding the distribution of chemicals in the environment is required to assess
exposure to humans and biota. The environmental transport of hydrophobic organic
contaminants such as polychlorinated biphenyls (PCBs), p,p'-DDT (l,l-bis(4-chlorophenyl)2,2,2-trichioroethane) and polycyclic aromatic hydrocarbons (PAHs) are dependent on their
distribution properties among various environmental phases. These distribution
characteristics are modeled by phase-distribution equilibrium constants such as water
solubility, octanol-water partition coefficient (K0), sorption coefficient (Kd or K0), vapor
pressure (Vp), and airwater partition coefficient (KH)(]). In aqueous environments, these
contaminants exist in diverse states in surface water. They can be freely dissolved in surface
water or associate with dissolved or particulate organic matter depending on their chemical
and physical properties (2). All of these forms can be transported by water or distributed
throughout surface water and their concentrations may exert adverse effects on aquatic
organisms and human health through multiple sources and pathways with variable and often
poorly understood factors.
The freely dissolved form of hydrophobic organic contaminants is considered
environmentally relevant to their bioavailability, toxicity, mobility and degradation processes
(3-5). It is the freely dissolved form of the contaminant which is transported across biological
membranes of aquatic organisms and potentially exerts toxic effects (2, 4, 5). A reduction in
the freely dissolved concentration of the contaminant refers directly to reduced
bioavailability. However, there is no clear distinction between the processes that control the
distribution of chemical contaminants in an environment and those that directly affect
bioavailability (6). Spatial and temporal factors, including seasonal changes in physical,
2
chemical and biological aspects of the aquatic ecosystem, may modify contaminant
bioavailability (i.e., aqueous activity and fugacity) and change the concentration available for
uptake by aquatic organisms. The potential uptake of toxic contaminants is affected by
changes of either the concentrations of the contaminant in the organism's immediate
environment or the environmental bioavailability of the contaminant (6).
Bioavailability is a key to deteiiiiining the nature of the exposure and the toxicity of a
chemical in the environment. However, it is a problematic parameter to measure.
Bioavailability, by definition, is determined by target concentrations in organisms (5). Any
chemical estimates of bioavailabiiity must be correlated with biological measures of
bioavailability or toxicological bioavailability (5). Recent developments in passive sampling
devices provide an alternative to understand chemical bioavailability (7). Instead of
measuring the total concentration in an environmental medium, the passive sampling
technique measures the concentration in a reference phase which can be brought into
equilibrium with the medium (7). The availability of a chemical is measured based on the
chemical potential which is logarithmically related to its fugacity and linearly related to its
freely dissolved concentration in a particular medium (7). As correlated with biological
concentrations, chemical estimates using passive sampling devices can predict toxicity and
can be used as a screening tool in the first tier of ecological risk assessment.
Identifying and measuring the chemical forms that are actually the bioavailable forms
is necessary to better understand the physical, chemical, and biological mechanisms that
control contaminant fates and effects in the aquatic environment. Advanced understanding of
bioavailable chemical distribution is required to predict accurately the fate and effects of
environmental contaminants and this knowledge can have substantial benefits for exposure
assessments and water-quality regulations. Despite the importance of environmental
bioavailability, very few studies have actually evaluated the distribution of chemical
bioavailability and the influencing factors in the field under different and often more variable
geochemical or physiological conditions than in the laboratory.
As a part of an assessment of the bioavailability of a chemical contaminant, the
ultimate goals of this dissertation were to understand the seasonal distribution of bioavailable
3
hydrophobic contaminants in surface water and to evaluate the potential environmental
factors influencing their bioavailability. In addition, further development of a passive
sampling device to measure bioavailable hydrophobic contaminants and field trial were
conducted and its efficiency was compared to a widely used passive sampling device. The
dissertation chapters are described below.
This chapter (Chapter 1) contains a general introduction providing background
information needed for the study. It contains the basic concept of bioavailability, passive
sampling technique, and general background of the target analytes and study area. The
dissertation hypotheses and objectives are present at the end of the chapter.
Chapter 2 presents the field study of distribution and seasonal variation of
bioavailable organochiorines in surface water using passive sampling techniques. The study
was carried out at the lower Willamette River at Portland Harbor, Oregon where surface
water runoff is determined by climatic influence and varies according to season (8). The
study area (River Mile 1 to 18) included the Portland Harbor superfund site (River Mile 3.5 to
9.5) and the McCormick Baxter superfund site (River Mile 7 East) (9). The potential
environmental factors influencing their bioavailable concentration distributions are discussed.
To screen the potential impacts associated with seasonal changes on aquatic organisms, the
bioavailable concentrations are compared to the national recommended water quality criteria
(10) and the Oregon water quality criteria (11).
Chapter 3 presents the further development of a passive sampling device. The field
trial of triolein-free low density polyethylene membrane was studied. Its efficiency was
compared to the widely used passive sampling device. The sampling rates and uptake model
for a wide range of hydrophobic contaminants are proposed.
Chapter 4 is part of a collaborative study of "Environmental stresses and skeleton
deformities in fish from the Willamette River, Oregon" (12). This chapter focuses only on the
distribution of bioavailable PCBs and organochiorine pesticides along specific sections of the
Willamette River (Newberg Pool, River Mile 44 to 47), where elevated frequencies of
skeletal deformities in fish were detected, relative to those in the upper river (Corvallis, River
4
Mile 135). The complete collaborative work has been published in Environmental Science
and Technology. Volume 39, No. 10, 2005, page 3495-3506, "Environmental stresses and
skeletal deformities injlshfrom the Willainette River, Oregon" (12), see Appendix E.
Chapter 5 summarizes the overall conclusion of this dissertation. The direction for
future work is also provided.
5
Background
Bioavailability. Bioavailability of a contaminant is specific to the exposure matrix,
duration of exposure, route of entry, and receptor. The concept of bioavailability consists of
three major components (13) as described in Figure 1.1. Environmental availability
represents the portion of the total material present in a compartment or compartments of the
environment which actually involves a particular process or group of processes and is subject
to modifying influences (13). However, the total amount of chemical potentially available is
not necessarily involved in a given process. Bioavailability is a special case of environmental
availability when organisms are involved in the process as a target. Bioavailability may be
described as the portion of the total quantity or concentration of a chemical in the
environment or a portion of it that is potentiaLly available for biological action, such as
uptake by an aquatic organism (14). Toxicological bioavailability is the fraction of the dose
absorbed by the organism which reaches the target sites in the organism or effective
intercellular concentration in the organism (13).
Environmental
availability
Environmental
bioavailability
Toxicological
bioavailability
Total
chemical
Sorbedl
sequestered
Freely
dissolved
Absoi
ion
Distribution
Metabolism
Excretion
Site of
toxic
action
Bioaccurnulation
Media
Exposure
Organism
Figure 1.1 Schematic representation of bioavailability as modified from Dickson et al. 1994
(13) and Wells and Lanno 200 1(15).
6
Water column
w, org
ingestion or ,'
excretion ,"
ingestion or
excretion
rnembrane'
transport
K11 or BCF
sorption!
desorption
mass transport
advective or
diffusive flux
qj
K0
"bou .ar layer"
sorption!
dcsorption
V
SV.
ti
K.or
sorption!
desorption
ingestion or
excretion
s, sq
C
sorptiol1!
A
desorption
oenihrane
transport
'..
doe
KdOC
KB or BCFY
,/
s, doe
mass transport
resuspension
"boun.ar Ia er"
sedimentation
;4
ingestion or
excretion
C s,org
Sediiient
Figure 1.2 A simple four-phase model describing the bioavailability and the partitioning
approach to the distribution of organic contaminant in water-sediment systems. The freely
dissolved fractions of the contaminants (Cw,aq and Cs, aq) are the most bioavailable. The
contribution from bound fractions (C,55, CW,d00, C,55 and C5, doe) may become important for
certain organism via ingestion as part of the food supply. The first subscript indicates the
environmental compartment; w = water, s = sediment. The second subscript refers to the
phase within that compartment; aq = aqueous (freely dissolved), org = organism, doc =
dissolved organic carbon, ss = suspended solids. (modified from Suffet et al. 1994 (2))
In aquatic systems, if the uptake through ingestion of food is excluded, the freely
dissolved fractions of organic contaminants are the most bioavailable (5). Organic chemicals
that are freely dissolved in the water, and not bound to or associated with organic matter, are
subject to diffusion transport across aquatic organism's membrane from the external aqueous
(2). Figure 1.2 illustrates a simple four-phase model describing the bioavailability and the
partitioning approach to the distribution of organic contaminant in water-sediment systems.
7
The aqueous concentration at equilibrium is related to the distribution coefficient (K) of the
various phases, assuming the interactions of the contaminant concentrations are at
equilibrium in the water column and sediment. Partitioning to sediments, and dissolved or
particulate organic matter decreases freely dissolved concentration of the contaminant and
thus the bioavailability of contaminants to biota (2, 5). Many factors can influence the
environmental availability including the environmental bioavailability by altering the
environmental distribution of the chemicals and this would consequently alter
bioconcentration and bioaccumulation (2, 6, 14). Physical factors include temperature,
advection, and sedimentation and resuspension. Physicochemical factors include dissolution,
desorption, diffusion, and degradation. Biological factors include diagenesis, organic matter
loading and bioturbation. However, there is no clear distinction between the processes that
control the distribution of chemical contaminants in an environment and those that directly
affect bioavailability (6).
Significance of spatial and seasonal aspects on chemical distribution. A
consideration of the spatial and seasonal aspects is essential to chemical exposure in
ecological risk assessment (16). These variables affect the concentrations available for uptake
from surrounding media by organisms. Several studies have indicated bioaccumulation of
PCBs and DDTs in fish and lower trophic level biota seasonally changed according to
concentrations of PCBs and DDTs in surrounding water and sediment (17, 18). As well, a
significant spatial and seasonal pattern in exposure modeling for human health risk estimates
for recreational fish consumers has been addressed (18). Consideration of spatial and
temporal characteristics of contaminant bioaccumulation in fish reduced risk estimates as
much as one order of magnitude lower than those obtained without the spatial and temporal
consideration. In addition to improving our understanding of the chemical fate and transport
in the environment, understanding and consideration of spatial and seasonal distribution of
contaminants can reduce uncertainty associated with chemical exposure and provide a
quantitative expression of the confidence in risk estimates. Consideration of spatial and
seasonal variation can help support the decision-making process for risk assessment and risk
management of contaminated water and sediment.
8
Spatial factors include sources of chemical contaminants, location of sensitive
biological resources, routes of exposure, and factors that may modify contaminant mobility
and availability (i.e., changing composition of sediment, abundance of microorganisms
involved in contaminant biodegradation) (19). Temporal factors include seasonal changes in
physical, chemical, or biological aspects of ecosystem that may impact the potential for
exposure (19). The influence of seasonal variation on contaminant concentration and load
may vary across a wide spectrum of the watershed characteristic. Foster et al. (20) reported
increased water movement during storm flow enhanced PCB, organochiorine pesticides, and
PAH riverine transport in both dissolved and particulate phase at the Susquenhanna River
Basin, Maryland, USA. Soderstrom et al. (21) observed increased concentrations of DDTs
and changes in DDD: DDE ratios (DDT metabolites) after snowmelt due to resuspension of
surface sediment in a eutrophic and an oligotrophic lake. By contrast, PCB concentrations in
the Eman River, Sweden were inversely related to river discharge due to dilution processes
(22). In addition, seasonal variation in physical or chemical parameters (i.e., temperature or
pH) can modify the bioavailability of contaminants and consequently change the nature of
exposure (19).
Although the spatial and seasonal distributions of chemical contaminants such as
PCBs and organochlorine pesticides have been widely studied, significant information gaps
exist for their seasonal bioavailability. It is the freely dissolved fraction, not particulate
fraction or dissolved fraction associated with dissolved organic matter, that is most
bioavailable and relevant to the internal concentrations of the target organisms (5). Because
PCBs and organochiorine pesticides are a problem of global concern, such information gaps
must be addressed to promote a more complete understanding of their bioavailability
characteristics that may be influenced by spatial and seasonal factors.
Passive sampling techniques as surrogates for evaluating bioavailability.
Bioavailability is the key to determining the nature of the exposure and the toxicity of a
chemical in the environment. Any chemical estimates of bioavailability must be correlated
with biological measures of bioavailability or toxicological bioavailability (5). Measuring
the actual dose or toxicant concentration at the target site is ideal for biologically effective
dose and toxicity assessment (5). Alternatively, whole body internal concentrations are
9
sufficiently good approximations of target-site concentrations for toxic chemicals (5).
However, measuring bioavailable chemicals in the exposed organisms in a field conditions
sometimes fails to accurately reflect environmental contaminant concentrations because of
residue metabolism and depuration and the effects of environmental stressors on organism
health (23).
Recent developments in passive sampling devices provide an alternative to
understand chemical bioavailability (7, 24, 25). These new developments in sampling
technique fit well into chemical uptake and bioconcentration / bioaccumulation in certain
aquatic organisms (5, 15, 25-27). Instead of measuring the total concentration in an
environmental medium, the passive sampling technique measures the concentration in a
reference phase which can be brought into equilibrium with the medium (7 28). The
availability of a chemical is measured based on the chemical potential which is
logarithmically related to its fugacity and linearly related to its freely dissolved concentration
in a particular medium (7, 28).
Figure 1.3 illustrates three uptake phases for a passive sampling device, which
includes the generalized uptake profile according to Equation 1 - a first-order kinetic model
(7):
Csampier (t)
=
Cmedium
kL. (1-
e2t)
(1)
where Csampier (t) is the concentration of the contaminant in the sampler as a function of time,
t, Cmedium is the concentration in the environmental medium, and k1 and k 2 are the uptake rate
and the elimination rate constants, respectively.
10
equiJibrium
C
O.5
Cu
C
U)
0
C
0
C.)
0
T112
time
Figure 1.3 Generalized uptake profile for a passive sampling device. The passive sampling
technique generally operates in three regimes: linear or kinetic, curvilinear or intermediate,
and equilibrium.
Low density polyethylene membranes, typically filled with triolein, have been
successfully deployed as passive sampling devices designed to accumulate nonpolar and
moderately polar organic contaminants from water, sediments, and air (15, 27, 29, 30). This
device is known as semipermeable membrane device (SPMD) introduced by Huckins et al.
(25). It Consists of polyethylene lay flat tubing containing a thin film of a neutral lipid,
95%
pure triolein (1,2,3-tri[cis-9-octadecenoyl]glycerol) (25). The diameters of the transient
cavities on polyethylene membrane range up to 10 A, which effectively preclude sampling of
any contaminant molecules associated with dissolved organic matter or particulates (31). It
has been proposed that the SPMD mimics key mechanisms of bioconcentration including
diffusing through biomembranes and partitioning between organism lipid and the
sunounding medium, but without metabolism (31). For example, uptake of organochiorine
contaminants was similar in SPMD, fish, and mussels (25-27). Determining
dissolvedlbioavailable concentrations with this technique would be a better measure to assess
bioconcentration / bioaccumulation factors in aquatic organisms as compared with filtered
water methodology, leading to a better prediction of environmental risk and risk assessment.
The three compartment model describing the mechanism for SPMD accumulation has
been established (28). The model consists of three compartments; water, polyethylene
membrane, and triolein, and three mass transfer step as described in Figure 1.4 by Gale (28).
11
Figure 1.4 shows a dissolved chemical is transported to the aqueous diffusion film via
turbulent-diffusive transport through the aqueous film and partioning into polyethylene
membrane, and diffusive transport through the polyethylene film, and partitioning between it
and the triolein. It is noted that polyethylene as a chemical reservoir in SPMD is accounted
for by the three compartment model and it is worth the effort to further develop it as an
alternative passive sampling device as present in Chapter 3.
A
Ditlusional SJow Steps c'
W-ter
PoteriiiI Biotirn
Ple h1orie
Trioer
Steps
Turbulent
transport
(rnxinç)
0
ii
Pnpor
lCl
t
eylow
1
n
Ti
[C)
n
[CL
Tr
B
Water
Potyethytene
Trioein
Figure 1.4 The three compartment model for contaminant accumulation by SPMD as
proposed by Gale, 1998 (28). A) Proposed passive sampling steps for SPMD accumulation.
B) The three compartment model consisting of water, polyethylene and triolein. Rate
constants for input into the water (k0),accurnulative mass transfer from water to polyethylene
(k), from polyethylene to triolein (kpT), and the corresponding clearance rate constants for
mass transfer from water to polyethylene (k) and from polyethylene to triolein (kT) are
shown with their respective anows.
(Figure is adapted from Gale, 1998)
12
The linear uptake model (Figure 1.3) is desired for the integrative sampling approach
for SPMD application (23). Huckins et al. (23) have derived the first order kinetic model
(Equation 1) to estimate bioavailable water concentrations from SPMD concentrations in the
linear uptake phase and can be rewritten as
=
-SPMD
Fl]
SPMD. Ilc
.
t
-1
(2)
where C'SPMD is the concentration of the bioavailable contaminant in the SPMD, MSPMD is the
mass of SPMD in grams R is the sampling rate in liters per day of a standard 1-g triolein
SPMD, and t is the exposure time is days.
Using Equation (2) and available Rç values (26, 32, 33), the bioavailable water
concentrations of hydrophobic contaminants can be estimated. For exposure conditions of
low to moderate flow/turbulence, SPMD uptake is under membrane control for compounds
with log K0 < 4.4 and under aqueous boundary layer control for compounds with log K0
4.4 (23). Thus the SPMD uptake of chemicals with log K0
4.4, which include most PCB
congeners, organochiorine pesticides, and PAHs, are sensitive to site hydrodynamics. SPMD
uptake rates are also affected by temperature and biofouling (34). Booij et al. (24) and
Huckins et al. (34) have developed the use of peiiiieability / performance reference
compound (PRC) to provide an overall correction factor for variations in SPMD uptake rates
under field condition.
Organochuorine compounds in aquatic system. Polychlorinated biphenyls (PCBs)
and organochiorine pesticides including p,p'-DDT and its metabolites (p,p'-DDD and p,p'DDE) and dieldrin are industrial and agricultural compounds. These compounds have
environmental significance because of their stability, toxicity, and tendency to accumulate in
lipids of organisms (35-37). Their production and use have been banned since 1970s. The
current major source of these compounds releases to air, water, and soil is from the cycling of
their residues remaining in the environment from one medium to another. Atmospheric
transport also plays an important role in long-range transport of organochiorines from their
initial source (38).
13
Organochiorine environmental transport varies depending on their chemical and
physical properties. Table 1.1 lists physicochemical properties of target PCBs and
organochiorine pesticides in this dissertation. Organochiorines exist in diverse states in
surface water. They can be freely dissolved in surface water or associated with dissolved or
particulate matter depending on their chemical and physical properties (35-37). All of these
forms can be transported by water or distributed throughout surface water. Their major
transport is mainly via waterborne particles but in a river containing small amount of
particles, their major transport can occur in the dissolved phase (35-37). In addition to
ingestion of PCBs or DDTs contaminated in the aquatic food chain, aquatic organisms (e.g.
fish, mollusk) directly uptake bioavailable form of these contaminants from surrounding
water into their body by passive diffusion through semipermeable membranes such as gill,
lining of the mouth, or gastrointestinal tract (35-37, 39). After uptake, organochiorine
contaminants are transported to different compartments of the body including sites of action,
metabolism, storage and excretion. The toxic effects of a contaminant can differ between
species, strains, sex and age groups (35, 36, 40).
DDT is highly toxic to aquatic organisms (35). Early developmental stages of fish
and aquatic invertebrate are more susceptible than adults to DDT (35). The acute toxicity of
p,p'-DDT to both vertebrates and invertebrates is attributed mainly to action upon axonal Na*
channels (41). Apart from the action upon Na channels, it has been reported that p,p'-DDT
can act upon the K channels and inhibit certain ATPase (4]). In fish, cellular respiration may
be the main toxic target of DDT due to the inhibition of ATPase which can affect
osmoregulation (35, 41). The effects of DDT on a range of physiological functions and
behavioral development in fish have been reported (35). It has been reported that DDT can
cause skeleton deformities by impairing developmental processes and bone formation in
certain fish species (42). Pathologic changes by DDT are also observed in the liver and
reproductive organs of laboratory animals (35).
14
Table 1.1 List of target PCBs and organochiorine pesticides and their physicochemical
properties at 20-25 °C
chemical
- Trichiorobiphenyls
PCB 37
- Tetrachiorobiphenyls
PCB 44
PCB49
water
solubility
(mg/L)a
Log K0 a
3,4,4'
1.5 x 102
2,2',3,5'
2,2',4,5'
2,2',5,5'
2,3,4,4'
chemical structure
PCB 52
PCB 60
PCB 74
2,4,4',S
PCB 77
3,3',4,4'
- Pentachiorobiphenyls
PCB 87
2,2',3,4,5'
PCB 99
2,2',4,4',5
PCB 101
2,2,4,5,5'
PCB 105
2,3,3',4,4'
PCB 114
2,3,4,4',5
PCB 118
2,3',4,4',5
PCB 126
3,3',4,4',5
- Hexachiorobiphenyls
PCB 128
2,2',3,3',4,4'
PCB 138
2,2',3,4,4',5'
PCB 153
2,2',4,4'5,5'
PCB 156
2,3,3',4,4',5
PCB 166
2,3,4,4',5,6
PCB 169
3,3',4,4',5,5'
Heptachiorobiphenyls
PCB 170
2,2',3,3',4,4',5
PCB 180
2,2',3,4,4',5,5'
PCB 183
2,2',3,4,4',5',6
PCB 187
2,2',3,4',5,5',6
PCB 189
2,3,3',4,4',5,5'
Organochlorine pesticides
sorption
coefficient,
log K0 a
vapor
pressure
5.9
4.8
4.5 x i0
1.0 x 10_i
6.0
6.1
6.1
6.3
6.7
6.5
4.7
5.7
3.9
5.7
6.4 x i0
1.6x102
3.0 x 10.2
4.0 x 102
NA
1.0 x i0
4.0 x i0
2
1.1 x 10
1.0 x 102
NA
NA
NA
NA
6.5
6.6
6.4
6.0
6.7
7.1
6.9
6.0 x 10
7.0
1.5 x i0
1.0 x i0
NA
NA
5.1 x 10
6.7
6.9
5.0 x i0
3.1 x i0
7.2
7.0
7.6
NA
4.4
(Pa
a
7.4x103
2.0 x i0
2.2 x 10
NA
2.0 x i0
5.7
5.7
5.7
NA
NA
NA
NA
2.3 x 10
5.3
5.9
5.9
NA
NA
6.6
3.4 x i0
5.0 x i0
7.0 x i0
1.5 x i0
3.5 x l0
NA
NA
NA
NA
NA
NA
5.4x i0
7.2
7.2
7.2
7.7
5.6
5.8
NA
5.5
NA
5.5 x i0
5.7
6.3
2.5 x 10
p,p'-DDD
2.0 x 102
6.1
5.0
1.3 x 10
p,p'-DDE
1 x 10'
6.0
4.7
8.7 x 10
dieldrin
2 x 10'
3.5
4.1
4.0 x iO4
p,p'-DDT
.
NA
4.0 x i0
NA
7.1
1.3 x 10
3.1 x i0
NA
9.4 x i0
NA
NA - not available
a Sources: Mackay et al. (43), Augustijn-Beckers et al. (44), Petty et al.(45), and Eisler and Belisle (46).
15
Dieldrin is highly toxic to aquatic crustaceans and fish (36). Several studies have
revealed that dieldrin toxicity increases with increasing temperature (36). It has been reported
that dieldrin can produce adverse enzymatic and hormona' change in fish that lead to
impaired reproductive ability (36). Different life stages of fish have been found to have
different susceptibility to dieldrin. Eggs were resistant and juvenile stages were less
susceptible than adults (36).
Many studies have reported PCB toxicity in both in vitro and in vivo studies (40).
The toxicity of individual PCBs is related to the molecular structure. The most potent
congeners are those that contain non-ortho or mono-ortho chlorine substituents, so called coplanar PCBs, which have a similar structure to 2,3,7,8-tetrachlorodibenzo-p-dioxin. These
dioxin-like PC]3s act upon aryl hydrocarbon (Ah) receptors, with consequent induction of
cytochrome P450 1A1/2 and Ah-receptor mediated toxicity (i.e. immunotoxicity, disruption
of multiples endocrine pathways, developmental toxicity, reproductive toxicity,
carcinogenicity, tumor promotion, hepatotoxicity) (40). Non-planar PCBs elicit toxic
responses including neurobehavioral, neurotoxic, carcinogenic and endocrine changes by
acting through multiple unrelated mechanisms (47).
Although the toxicology of PCBs has been studied extensively, the degree of toxicity
and nature of the effects remain highly debatable. The complexity of PCB contamination
with the possibility of interactive effects between different congeners andlor with other
persistent contaminants have made ecological effects of PCBs difficult to prove (41).
Recently, the influence of PCBs on the endocrine system has been a subject of particular
environmental interest. Aquatic communities may be susceptible to endocrine disruption due
to their association with PCB contaminated sediments and surface water. Many studies have
suggested PCBs adversely affected gonadal development, vitellogenin expression, thyroid
function and sexual differentiation in aquatic organisms (37, 40, 46, 48). It has been
suggested that the decline in certain fish populations may be associated with developmental
and reproductive impairment caused by PCBs (48).
Study area: the lower Willamette River at Portland Harbor, Oregon. The
Willamette River in western Oregon is one of only 14 American Heritage Designated Rivers
16
(49). The river has the thirteen the largest stream flow in the United States and yields more
runoff per square mile than any other large river in the US (50). The Willamette River flows
approximately 187 miles northward through Portland, Oregon's largest metropolitan area,
before joining the Columbia River. After this joining, the Columbia River flows an additional
100 miles westward to the Pacific Ocean. The Willamette River provides a significant
migratory corridor, nursery habitat and adult forage for runs of salmon, and nearly 50 species
of fish have been identified in the river (51). Recreational and sport fishing are extremely
popular throughout the lower Willamette basin. Most development along the Willamette
River has been located within the Portland Harbor. Portland Harbor is heavily industrialized,
and contains a multitude of facilities and both private and municipal waste water outfalls.
The harbor generally has a low sediment transport capacity (8). Surface water runoffs are
determined by climate influence and vary according to season (8).
The presence of PCBs, pesticides, PAHs, dioxins/furans, arsenic, cadmium,
chromium, copper, lead, mercury, zinc, organotins, pentachiorophenol, and solvents has been
demonstrated in Portland Harbor sediment within a six-mile stretch from the southern tip of
Sauvie Island to Swan Island (RM 3.5 RM 9.5)(8). These contaminants may have entered
the river via spillage during product shipping and handling, direct disposal or discharge,
accidental spills, contaminated ground water discharge, surface water runoff, stormwater
discharge, or contaminated soil erosion (52). These contaminants can pose risks to people,
fish and other wildlife and the detected levels were high enough to place Portland Harbor on
the Federal National Priority List (NPL, commonly known as superfund) (52). The NPL is
the US Environmental Protection Agency (EPA)'s list of the national most contaminated
hazardous waste sites which may pose dangers to public health and the environment and are
therefore targeted for cleanup (9). Portland Harbor became a superfund site on December 1,
2000 (9). The area covers the six-mile stretch between the southern tip of Sauvie Island to
Swan Island (RM 3.5 RM 9.5) and contains McCormick and Baxter Creosoting Co.
(Portland plant) superfund site.
Our previous study found PCB and DDT residues accumulated in three recreational
fish species from the Portland Harbor exceeded the US EPA fish advisory's screening values
and potentially posed adverse health effects to the recreational and subsistence fishers (53,
17
54). Bioaccumulation of PCBs and DDTs in fish is related to the concentrations of PCBs and
DDTs in surrounding water and sediment and can change seasonally (17 18). Consequently,
the seasonal pattern in exposure modeling for environmental and human health risk
assessment can affect the accuracy of risk estimates (18). As surface water runoffs within the
harbor are determined by climate influence and vary according to season (8), PCB and DDT
river concentrations, particularly the bioavailable concentrations may change seasonally and
consequently change the nature of exposure. This can affect both aquatic organisms and
human healTh. The river characteristics make Portland Harbor an excellent candidate for
studying the seasonal bioavailability of PCBs and organochiorine pesticides in surface water.
Hypotheses and objectives
Hypothesis 1. The water concentrations of bioavailable organochiorines including PCBs,
p,p'-DDT and its metabolites (p,p'-DDD and p,p'-DDE), and dieldrin change seasonally
(Chapter 2).
Objectives
- To determine the bioavailable concentrations of organochlorines in surface water using
passive sampling device
- To evaluate the spatial influence on the distribution of bioavailable organochiorines in
surface water
- To evaluate the seasonal distribution of bioavailable organochiorines in surface water and to
assess the potential factors influencing their seasonal concentrations
Hypothesis 2. Seasonal changes affect the nature of exposure to organochlorines in surface
water by aquatic organisms and local fishers who consume fish in the study area (Chapter 2).
Objective
- To screen the potential impacts associated with seasonal changes on aquatic organisms and
local fish consumers by comparing seasonal concentrations of bioavailable organochiorines
to the national recommended water quality criteria (10) and the Oregon water quality criteria
(11)
18
Hypothesis 3. The solvent- free low density polyethylene membrane lay flat tubing (LFT) is
as efficient as the widely used passive sampling device in sampling bioavailable hydrophobic
organic contaminants in surface water (Chapter 3).
Objectives
- To evaluate the use of LFT as an alternative device for monitoring bioavailable
hydrophobic organic contaminants in surface water
- To compare the efficiency of LFT with the semipeimeable membrane device (SPMD)
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23
CHAPTER 2
EVALUATION OF SEASONAL BIOAVAILABILITY OF
ORGANOCHLORINE PESTICIDES AND PCBs AT A SUPERFUND SITE
USING PASSIVE SAMPLING DEVICES
Sethajintanin, D.1 and Anderson, K.A
1,2
Department of Environmental and Molecular Toxicology
2
Food Safety and Environmental Stewardship Program,
Oregon State University, Corvallis, Oregon 97331
24
Abstract
Although the spatial and seasonal distribution of polychiorinated biphenyls (PCBs)
and organochiorine pesticides (i.e., DDT, dieldrin) have been widely studied, significant
information gaps exist for their bioavailability. Because PCBs and organochiorine pesticides
are a problem of global concern, such information gaps must be addressed to promote a more
complete understanding of their bioavailability characteristics that may influence spatial and
seasonal factors, The present study focused on the spatial and seasonal distribution of
bioavailable organochiorine pesticides and PCBs within the surface water of a contaminated
harbor. Passive sampling devices were intensively deployed just outside the shipping channel
adjacent to various land uses on the lower Willamette River, Oregon including Portland
Harbor superfund site in summer and fall during 2001-2004. An increase of estimated
bioavailable DDTs (sum of p, p'-DDT, p, p'-DDD, and p,p'-DDE) concentrations was
strongly affected by the local historic productions of DDTs and seasonal changes in river
conditions. The dominance of bioavailable p, p'-DDD and high DDD/DDE ratios observed
during periods of low flow in summer suggested direct inputs of p, p' -DDD and conditions
favoring reductive dechlorination of p, p'-DDT top, p'-DDD. The estimated bioavailable
concentrations and daily loads of PCJ3s and dieldrin increased during periods of high
precipitation, high river flow in fall, especially during episodic rainstorms. The similarity of
PCB congener profiles and PCB homolog ratios at the industrial area and at the
urban/residential areas suggested the local sources of PCBs at the industrial area were
important enough to significantly increase the concentrations of bioavailable PCBs in surface
water but not so substantial as to change composition relative to surface water inputs from
upstream. Bioavailable concentrations organochlorine compounds seasonally exceeded the
national and the Oregon water quality criteria. These seasonal exceedances suggest the
potential impacts associated with seasonal changes of bioavailable organochiorine
distributions in surface waters and the significances of considering realistic seasonal and site-
specific conditions in risk assessment and water quality management.
Keywords Willamette River
bioavailability
organochiorines contaminants
seasonal influence
25
Introduction
The freely dissolved form of hydrophobic organic contaminants is considered
environmentally relevant to their bioavailability, toxicity, mobility and degradation processes
(1-3). It is the freely dissolved form of the contaminant which is transported across biological
membranes of aquatic organisms and potentially exerts toxic effects (2-4). A reduction in the
freely dissolved concentration of the contaminant refers directly to reduced bioavailability,
and vice versa. However, there is no clear distinction between the process that controls the
distribution of chemical contaminants in an environment and those that directly affect
bioavailability (5). Spatial and temporal factors including seasonal changes in physical,
chemical and biological aspects of the aquatic ecosystem may modify contaminant
bioavailability and this changes concentration available for uptake from water by aquatic
organisms. The potential uptake of toxic contaminants is affected by changes in either the
concentrations of the contaminant in the organism's immediate environment or the
environmental bioavailability of the contaminant (5). Despite the importance of
environmental bioavailability, very few studies have actually evaluated the distribution of
chemical bioavailability and the influencing factors in the field under different and often
more variable geochemical or physiological conditions than in the laboratory.
A consideration of the spatial and seasonal aspects is essential to chemical exposure
in ecological risk assessment (6). These variables affect the concentrations available for
uptake from surrounding media by organisms. Several studies have indicated
bioaccumulation of polychiorinated biphenyls (PCBs) and DDTs (1,1-bis(4-chlorophenyl)2,2,2-trichioroethane and its metabolites) in fish and lower trophic level biota seasonally
changed according to concentrations of PCI3s and DDTs in surrounding water and sediment
(7, 8). As well, a significant spatial and seasonal pattern in exposure modeling for human
health risk estimates for recreational fish consumers has been addressed (8). Consideration of
spatial and temporal characteristics of contaminant bioaccumulation in fish reduced risk
estimates as much as 1 order of magnitude lower than those obtained without the spatial and
temporal consideration. In addition to improving our understanding of chemical fate and
transport in the environment, understanding and consideration of spatial and seasonal
distribution of contaminants can reduce uncertainty associated with chemical exposure and
26
provide a quantitative expression of the confidence in risk estimates. Consideration of spatial
and seasonal variation can help support the decision-making process for risk assessment and
risk management of contaminated water and sediment.
Spatial factors include sources of chemical contaminants, location of sensitive
biological resources, routes of exposure, and factors that may modify contaminant mobility
and availability (9). Temporal factors includes seasonal changes in physical, chemical, or
biological aspects of ecosystem that may be a potential for exposure (9). The influence of
seasonal variation on contaminant concentration and load may vary across a wide spectrum
of watershed characteristic. Foster et al. (10) reported increased water movement during
storm flow enhanced transport of PCBs, organochiorine pesticides, and polycyclic aromatic
hydrocarbons (PAHs) in both dissolved and particulate phase at the Susquenhanna River
Basin, Maryland, USA. Soderstrom et al. (11) observed increased concentrations of DDTs
and changes in DDD: DDE ratios after snowmelt due to resuspension of surface sediment in
a eutrophic and an oligotrophic lake. By contrast, PCB concentrations in the Eman River,
Sweden were inversely related to river discharge due to dilution process (12). In addition,
seasonal variation in physical or chemical parameters (i.e., temperature or pH) can modify
the bioavailability of contaminants and consequently change the nature of exposure (9).
Although the spatial and seasonal distributions of chemical contaminants such as PCBs and
DDTs have been widely studied, significant information gaps exist for their seasonal
bioavailability. Because PCBs and organochiorine pesticides are a problem of global
concern, such information gaps must be addressed to promote a more complete
understanding of their bioavailability characteristics that may be influenced by spatial and
seasonal factors.
The Willamette River in western Oregon is one of only 14 American Heritage
Designated Rivers (13). The river has the thirteenth largest stream flow in the US and yields
more runoff per square mile than any other large river in the US (14). Recreational and sport
fishing are extremely popular throughout the lower Willamette basin. The lower end of the
Willamette River, Portland Harbor, is heavily industrialized and contains a multitude of
facilities and both private and municipal waste water outfalls. The lower Willamette River at
Portland Harbor is deep, slow moving, and tidally influenced (15). Due to elevated
27
concentrations of PCBs, organochiorine pesticides, dioxins/furans, PAHs, and heavy metals
in the harbor sediment, Portland Harbor has been placed in the Federal National Priority List
(NPL), commonly known as superfund (16).
Our previous study found PCB and DDT residues accumulated in three recreational
fish species from the Portland Harbor exceeded the US EPA fish advisory's screening values
and potentially posed adverse health effects to the recreational and subsistence fishers (17,
18). Bioaccumulation of PCBs and DDTs in fish is related to the concentrations of PCBs and
DDTs in surrounding water and sediment and can change seasonally (7 8). As surface water
runoffs within the harbor are determined by climate influence and vary according to season
(15), PCB and DDT river concentrations, particularly the bioavailable concentrations may
change seasonally and consequently change the nature of exposure. The consequence can
affect both aquatic organisms and human health. The river characteristics make Portland
Harbor an ideal study area for evaluating seasonal bioavailability of PCBs and
organochiorine pesticides in surface water.
The ultimate goals of this study were to understand the seasonal distribution of
bioavailable PCBs, p,p'-DDT and its derivatives, and dieldrin in surface water and to
evaluate the potential environmental factors influencing their bioavailability. The passive
sampling technique using semipermeable membrane device (SPMD) (19, 20) was chosen to
get a time-integrated measure of their bioavailable fraction. The SPMD consists of
polyethylene lay flat tubing containing a thin film of a neutral lipid,
95% pure triolein
(l,2,3-tri[cis-9-octadecenoyl]glycerol) (21). It has been proposed that SPMD mimics key
mechanisms of bioconcentration including diffusing through biomembranes and partitioning
between organism lipid and the surrounding medium , but without metabolism (19). In this
work, the influences of seasonal and episodic events coupled with in situ water chemistry on
their bioavailable transport were intensively investigated. The potential environmental factors
influencing their bioavailability were discussed. To screen the potential impacts associated
with seasonal changes on aquatic organisms, the bioavailable concentrations were compared
to the national recommended water quality criteria (22) and the Oregon water quality criteria
(23).
28
Materials and Methods
Materials and chemicals. Standard SPMDs were purchased from Environmental
Sampling Technologies (EST, St. Joseph, MO). Standards of organochiorine pesticides
(purities
98.5%) and PCBs (purities
99%) were from Chem Service, Inc. (West Chester,
PA) and AccuStandard (New Haven, CT), respectively. All solvents used were pesticide or
Optima® grade from Fisher Scientific (Fairlawn, NJ). Certified reference material of PCB
congeners and organochlorine pesticides in cod liver oil (SRM 1588a) was purchased from
the National Institute of Standards and Technology (NIST, Gaithersburg, MD). SRM 1588a
was used for method validity and accuracy purposes for the determination of PCBs and
organochlorine pesticides in complex lipophilic matrices such as triolein.
Selection of 25 target PCB congeners were based on their toxicity, frequency of
occurrence, and abundance in environmental matrices (24). Target PCB congeners included
dioxin-like congeners (tetra-C13; PCB 77, penta-CB; PCB 105, PCB 114, PCB 118, PCB
126; hexa-CB; PCB 156, PCB 169; hepta.-CB; PCB 189) and non dioxin-like congeners (tn-
CB; PCB 37, tetra-CB; PCB 44, PCB 49, PCB 52, PCB 60, PCB 74, penta-CB; PCB 87, PCB
99, PCB 101, hexa-CB; PCB 128, PCB 138, PCB 153, PCB 166, hepta-CB; PCB 170, PCB
180, PCB 183, PCB 187). Target organochiorine pesticides were p,p'-DDT, p,p'-DDD,
p,p'DDE, and dieldrin.
Study area. The sampling areas were located at the lower Willamette River at
Portland Harbor from River Mile 1 to 18 and contained the Portland Harbor superfund site
(River Mile 3.5 to 9.5) and the McCoiiiiick and Baxter Creosoting Co. (Portland plant)
superfund site (River Mile 7 East). The sampling sites were outside the main shipping
channel and often near stream outlets of various upstream land uses. The eleven sampling
sites (Figure 1) were at River Mile 1 East (Columbia Slough; industrial area), River Mile 3.5
West (Sauvie Island at Multnomah Channel; industrial and urban area), River Mile 3.5 East
(opposite to Multnomah Channel; industrial area) , River Mile 7 West (Railroad Bridge;
industrial area), River Mile 7 East (McCormick and Baxter superfund site), River Mile 8 East
(Swan Island; industrial area), River Mile 12 East (under Steel Bridge! Interstate 5 Highway;
downtown/urban area), River Mile 13 West (Hawthorne Bridge; downtown/urban area),
29
River Mile 15 East (Ross Island: a sand and gravel operation! undeveloped area), River Mile
17 East (golf course, park), and River Mile 18 West (Mouth of Johnson Creek;
urban/agricultural creek, residential area).
The Willamette Basin
\wasngton
Portland
ci,
0
0
0
(ti
0
0
0
--Swan Island
V
Oregn
I
"aipPortIand
-
aliforni. 'Nevada
12
RM 13"
I
1
L
0
0
4
15
rRM l5'c,
RM1
RM18
sampling site
2
-'
-'
Ross
Island
-
't
tim fN
10km
Figure 2.1 The lower Willamette River at Portland, Oregon, showing locations of the
sampling sites (RM = river mile)
Sources of precipitation and stream flow data. Precipitation and stream flow data
were needed to characterize the river conditions during sample collection. Precipitation data
were obtained from the National Weather Service Forecast Office - Portland, OR (25). The
station was located at the Portland International Airport which was 9 miles northeast of
downtown Portland. Stream flow data recorded at River Mile 12.8 were obtained from the
US Geological Survey (26). Stream flow data were also used to convert estimated surface
water concentrations using SPMD into loading estimates. A daily mass load was calculated
by multiplying the estimated river concentration using SPMD by the average daily flow rate
through the river.
30
Sample collection. Five individual SPMDs were loaded in a flow-through stainless
steel cage. Each cage was submerged approximately 10 ft from the river bottom and was
suspended with "anchor-cable-cage-cable-float" arrangement. The river depth at sampling
locations ranged from 2-50 ft. At the sampling sites at RM 7 East where the river was
generally less than 10 ft. deep, the samplers were suspended below water surface but above
the sediment. SPMDs were deployed for 7-21 days. Water temperature and other water
chemistry parameters (dissolved oxygen, specific conductivity, oxidation-reduction potential,
pH, NH4tN, and NO3 -N concentrations) were measured during deployment and retrieval
using an YSI 6920 SONDE (Yellow Springs, OH). The average temperature ranged from 9 to
22 °C. Water samples were also collected for the analysis of total organic carbon (TOC),
dissolved organic carbon (DOC), total suspended solids (TSS), and total dissolved solids
(TDS).
On retrieval, SPMDs were cleaned by gently rubbing with gloved hands in on-site
water, then rinsed in iN HC1 (Trace metal grade, Fisher Chemical, Fairlawn, NJ), 18 M2cm
water, acetone (Pesticide grade, Fisher Scientific, Fairlawn, NJ), and isopropanol (Pesticide
grade, Fisher Scientific, Fairlawn, NJ), respectively. Cleaned SPMDs were kept in clean
glass amber jars and transported on ice-packs. Samples were stored at -20 °C until analysis.
Sample extraction and chemical analysis. SPMD extraction and cleanup were
based on established protocols and only modified slightly as necessary (19, 27). SPMDs were
dialyzed in hexanes, 400 mL for 5 SPMDs (Pesticide grade, Fisher Scientific, Fairlawn, NJ)
for 18 hr, followed by a second dialysis with fresh hexanes for 6 hr. The combined dialysates
were concentrated by rotary evaporation and a TurboVap® LV evaporator (Zymark®,
Hopkinton, MA). The samples were cleaned and fractionated using gel permeation
chromatography (Waters® gel permeation chromatography cleanup system; Water® 515
HPLC pump, 717 Plus autosampler, 2487 dual X absorbance detector, and fraction collector
II, Milford, MA) with dichloromethane (Optima®, Fisher Scientific, Fairlawn, NJ) as the
mobile phase at the flow rate of 5 mL/min. Appropriate fractions were determined by
analyzing standards and fortified samples. The appropriate fraction (14-20 mm) was collected
and split into two equal sub-fractions: 1) PCB and organochlorine pesticides for this study 2)
PAHs for another study. PCB and organochlorine pesticide fraction was subjected to volume
31
reduction using a TurboVap® LV evaporator and solvent exchanged into iso-octane
(Pesticide grade, Fisher Scientific, Fairlawn, NJ) with a final volume of 1 mL.
PCB congeners and OC pesticides were deteiiiiined using GC-ECD (Agilent
Technologies 6890N Network GC system, Palo Alto, CA) dual capillary columns (db-xlb and
db-17 with length 30 m, i.d. 0.25 mm, and film thickness 0.25 Itm, J&W Scientific Inc.,
Agilent Technologies, Palo Alto, CA) Idual detectors. Injector and detector temperature were
at 250 °C, and 350 °C, respectively. The GC system was operated with helium carrier gas and
nitrogen makeup gas. The oven temperature program was as follows: 100 °C (1 mm) and
increased at 1.2 OCminl to 265 °C (2 mm).
Field duplicates and blanks (trip blank, field blanks, and field extraction blanks)
accompanying the deployed passive sampling devices during deployment, retrieval, and
transportation to the laboratory were included in every batch. These field blanks and
laboratory control blanks (i.e., procedural blanks, laboratory SPMD controls, fortified
samples, and standard reference material) represented 30 to 40% of a sample set and were
processed and analyzed exactly as the deployed samples. The method detection limits (MDL)
were determined as three times the heights of coincident peaks observed for each compound
in the laboratory SPMD control. For those analytes having no coincident peak, the MDLs
were set at a value equivalent to the lowest standard in the respective calibration curve.
Because contaminant uptake rates by SPMDs can change due to changes in
temperature, flow velocity of the surrounding water and buildup of periphyton on the
membrane surface, an in situ measurement to account for these field variables is needed (28,
29). PCB 8, PCB 82 and endrin were used as permeability/performance reference compounds
(PRCs) to measure the overall variations in SPMD uptake rates under field conditions. PRCs
are analytically non-interfering compounds with moderate to relatively high fugacity from
SPMDs and have physico-chemical properties similar to the target analytes, which are added
to the SPMDs prior to sealing the membrane tubes (29). Because both the uptake and the
dissipation of organic chemicals are controlled by the same molecular processes, in situ
dissipation rates of PRCs would allow for estimating in situ SPMD uptake rates under
32
various field conditions (28, 29). The PRC approach has been well described by Booij et al.
(28) and Huckins et al.(29).
None of the target analytes were identified in field blanks and laboratory control
blanks. The average percent recoveries of fortified samples were as follows: PCBs 69 ± 43%,
p,p'-DDT 71 ± 27%, p,p'-DDD 80 ± 21%, p,p'-DDE 66 ±16%, and dieldrin 73 ± 18%. The
average percent recoveries in certified reference material were as follows: PCBs 94 ± 26%,
p,p'-DDT 98 ± 18%, p,p'-DDD 105 ±17%, p,p'-DDE 76 ± 16% and deildrin 89 ± 6%.
Data analysis. The basic theory and mathematical models required for estimation of
analyte water concentrations from the concentrations in the SPMD have been described by
Huckins et al. (20). The average percent recoveries of PRCs in the deployed SPMDs
indicated the linear uptake model could be assumed for all target analytes in this study.
Differences in exposure temperature were corrected by using established SPMD sampling
rates (R) for PCBs and organochiorine pesticides at multiple temperatures (30-32). The small
variations of PRC dissipation rates among sampling sites and under different field seasons
suggested the effects of membrane biofouling and flow velocity-turbulence at the membrane
surface were considered negligible.
Estimates of water concentrations (Cm) from SPMD concentrations were calculated
by the following equation (20),
C
= CSPMD 'MSPMD 'R,
where C SPMD is the concentration of the individual analyte in the SPMD, MSPMD is the mass
of SPMD in grams, MSPMD is the sampling rate of a standard 1-g triolein SPMD, and t is the
time in days.
Data interpretation was performed using SPSS® Version 10.0.1(SPSS Inc., 19891999), Sigma Plot 2002 for Windows Version 8.0 (SPSS Inc., 1986-200 1), and Microsoft®
Office Excel 2003 (Microsoft Corporation, 1985-2003). Standard descriptive statistics, two
sample t-test and linear regression techniques were used to examine seasonal bioavailable
33
organochiorine concentrations and influence variables. Statistical analyses were considered
significant atp
0.05.
Estimates of bioavailable concentrations in surface waters were compared to the
national recommended water quality criteria (22) and the Oregon water quality criteria (23).
These guidelines were used as a screening tool to assess potential impacts associated with
seasonal or episodic changes of contaminant distributions in surface waters. Fresh water
aquatic life criteria are to protect the aquatic communities from toxic effects resulting from
chronic exposure to toxic contaminants in water (22). This criterion concentration is an
estimate of the highest concentration in surface water to which an aquatic community can be
exposed without resulting in an unacceptable effect. Human health water quality criteria are
to protect local fishers based on a 106 increased lifetime cancer risk from consumption of
fish and shellfish from the concerning areas(22).
Results and Discussions
River conditions and water chemistry. The lower Willamette River at Portland
Harbor could be typically characterized by seasonally defined conditions. We categorized the
river conditions according to the average river flow, total precipitation, and average
temperature during sample deployments. Over the sample deployment interval from 2001 to
2004, the river was categorized into low flow/low precipitation in summer (average river
flow < 10,000 ft3 Is, total precipitation 0-1 in., average temperature
20 °C) and high
flow/high precipitation in fall (average river flow> 10,000 ft3 /s, total precipitation> 1 in.,
average temperature <20 °C). In addition, any intermittent precipitation or high river flow
that occurred during sample deployment was considered as an episodic event in the present
study.
34
Table 2.1 Summary of river conditions and water chemistry parameters at Portland Harbor
during SPMD deployment.
river
total
water
flow
rain
temp.
(ft3/s)
(in.)
(°C)
08/02/01-
7000
0
22
7.4
08/16/01
(170)
(0.57)
09/13/01-
7200
09/20/01
(130)
10/16/01-
13000
11/06/01
(4000)
11/06/01-
27000
sampling
event
11126101b,c
0
2.93
07/17/02-
8800
08/07/02
(190)
08/07/02-
8400
08/21/02
(180)
09/11/02-
9600
09/25/02
(400)
11/07/02-
11000
11/26/02
(2000)
10/01/03-
10000
10115103b,
(620)
11/05/03-
14000
11/24/03c
(4800)
07/08/0407/29/04b
8300
(390)
08/19/04-
10000
09/09/04bC
(1700)
10/19/04-
21000
11/09/04c
(4700)
DO
ORP
NH4-N
NO3-N
(mg/L)
(mV)
(mgIL)
(mg/L)
0.12
7.2
140
0.054
2.1
(0.15)
(0.022)
(0.44)
(24)
(0.097)
(0.24)
20
7.4
0.11
8.6
210
0.12
2.2
(0.19)
(0.17)
(0.022)
(0.43)
(23)
(0.030)
(0.19)
13
7.4
0.096
11
200
0.14
1.4
(0.40)
(0.13)
(0.034)
(0.15)
(25)
(0.046)
(0.24)
10
7.4
0.12
12
210
0.14
1.7
(0.14)
(0.066)
(0.027)
(0.41)
(14)
(0.024)
(0.18)
22
7.4
0.17
8.7
160
0.25
2.1
(0.37)
(0.14)
(0.19)
(0.63)
(22)
(0.14)
(0.66)
22
7.3
0.19
8.3
150
0.25
2.0
(0.35)
(0.17)
(0.25)
(0.63)
(29)
(0.18)
(0.70)
19
7.4
0.098
9.3
160
0.21
1.6
(0.76)
(0.079)
(0.015)
(0.44)
(28)
(0.021)
(0.49)
9.5
7.2
0.078
12
160
0.18
1,3
(0.46)
(0.11)
(0.016)
(0.17)
(12)
(0.017)
(0.40)
18
7.2
0.10
10
280
0.24
0.62
(0.22)
(0.18)
(0.017)
(0.86)
(23)
(0.034)
(0.094)
9.0
NA
NA
NA
NA
NA
NA
23
7.2
0.097
9.5
160
0.032
0.75
(0.85)
(0.10)
(0.011)
(1.2)
(28)
(0.017)
(0.18)
22
7.2
0.10
8.5
170
0.16
0.57
(0.26)
(0.051)
(0.018)
(1.2)
(28)
(0.028)
(0.12)
9.6
6.4a
0.078
12
310
0.17
0.16
(1.0)
(0.13)
(0.018)
(0.49)
(127)
(0.045)
(0.10)
3.86
(19000)
0.04
0
0.41
1.88
2.32
2.71
specific
pH
conductivity
(mS/cm)
(1.0)
0.04
2.35
2.00
values are average of 11 sampling sites; numbers in parenthesis are 1 SD; NA - data not available
a lower pH was measured at River Mile 3.5 East (pH = 4.2) and RM Mile 7 West (pH = 5.1). There was no
overt failure of the probe. These two measurements appeared to be an outlier and we did not include to the
average; b sewage overflow occurred before or during sample deployment; C rainstorm during sample
deployment
35
Table 2.2 Summary results of total organic carbon (TOC), dissolved organic carbon (DOC),
total suspended solids (TSS), and total dissolved solids (TDS) at the Willamette River,
Oregon during SPMD deployments.
sampling
date
11/27/01
11/26/02
10/0 1/03
11/05/03
07/08/04
07/29/04
08/19/04
09/09/04
TOC
(mg/L)
2.4
(0.47)
2.2
(0.81)
DOC
(mg/L)
TSS
(mg/L)
TDS
(mg/L)
NA
NA
NA
NA
NA
NA
NA
4.2
(1.2)
6.8
(1.3)
7.8
(2.6)
7.8
(6.5)
6.8
(3.4)
120
(24)
66
(9.3)
94
(30)
86
(9.0)
74
(9,7)
2.1
(0.83)
1.4
1.3
(0.0058)
(0.044)
1.6
1.6
(0.058)
(0.050)
1.7
1.8
(0.21)
(0.27)
1.9
1.9
(0.21)
(0.17)
1.7
1.8
(0.073)
(0.093)
1.8
1.7
(0.076)
(0.060)
- Values are averages of 10 sampling sites (River Mile 1 - 18) in 2001, and 4 sampling sites (River Mile 1,
River Mile 7 West, River Mile 7 East, and River Mile 18) in 2002, 2003, and 2004. Spatial differences
between sampling sites were not statistically significant, therefore the data were averaged.
- Numbers in parenthesis are 1 SD
- NA; data not available
The river characteristics and water chemistry during passive sampling device
deployments are summarized in Table 2.1. In situ river physico-chemical parameters were
collected at the river bottom, at 10 ft. from the river bottom where the samplers were located,
and at the river surface. At each sampling site, water chemistry parameters of the three
vertical levels were not statistically different within a sampling event. Also within the study
area (18 miles), there was no statistical difference between the sampling sites. The physicochemical properties measured at 10 ft. from the river bottom at the eleven sampling sites
were therefore averaged and reported in Table 2.1. The difference in water temperature in
summer and fall was approximately 10 °C. Dissolved oxygen concentrations ranged from 7.2
mg/L in summer to 12 mg/L in fall. The river pH was neutral. The oxidation-reduction
potential tended to decrease in periods of low flow in summer (p = 0.054, t-test). There was
no seasonal pattern observed for the river specific conductivity, NH4tN, and NO3 -N
36
concentrations. In addition, the concentrations of TOC, DOC, TSS, and TDS did not change
seasonally (Table 2.2) which suggested that a major transport of contaminants in the lower
Willamette River was in the aqueous phase. The study of aqueous phase bioavailable
contaminant distribution in the present study is therefore relevant to temporal river
contaminant characterization.
Distributions of bioavailable DDT concentrations and potential sources.
Bioavailable DDT concentrations (sum of p, p'-DDT, p, p'-DDD, and p, p'-DDE; below
detection limits were treated as zero) from the eleven sampling sites over the four-year study
period varied from 27 pg/L to 1500 pg/L with an average concentration of 190 pgIL. The
highest concentrations were always observed at River Mile 7 West (350-1,500 pgIL). The
concentrations of DDTs in the Willamette River at River Mile 7 West were generally higher
than dissolved DDT concentrations of several other large rivers in the US including the San
Joaquin River, California (< 1,000 pgIL) (33), the Missouri River, Missouri (27-270 pgIL)
(34), and the Susquehanna River, Maryland (280 pg/L) (10). However they were comparable
to or much lower than the concentrations in several rivers in other parts of the world such as
the Humber catchments, UK; 220 - 1,800 pgIL(35), the Minjiang River, China; 40,000230,000 pg/L (36) and the Kafue River, Zambia; 7,000-35,000 pg/L (37). It is important to
note that only the studies at the Missouri River and the Kafue River used passive sampling
devices to study the dissolved concentrations while the other studies used conventional
filtered water methodology. The two approaches are not directly comparable since, unlike the
passive sampling technique, the dissolved concentrations in filtered waters would include
DDTs associated with dissolved organic matter. Therefore the non-passive sampling device
technique may overestimate the truly dissolved bioavailable concentrations. However, in
general, the Willamette River at Portland Harbor, particularly at River Mile 7 West is more
contaminated with DDTs than many studied compromised rivers in the US, but it is generally
less than compromised rives worldwide.
Figure 2.2 shows the average concentrations of DDTs estimated from DDT
concentrations in the SPMD. Spatial distribution of DDTs was observed both in summer
and fall conditions. Bioavailable concentrations of DDTs and each individual p, p'-homolog
37
at River Mile 7 West were significantly higher than any other sampling sites in both summer
and fall (p <0.001; ANOVA F-test and Tukey's HSD). The concentrations of bioavailable
DDTs downstream of River Mile 7 west were apparently diluted from the concentrations
measured at River Mile 7 West. The average bioavailable DDT concentrations at the
upstream sampling sites including River Mile 7 East were approximately 10-fold less than
those at River Mile 7 West (Figure 2.2).
DDT production and use in the US has been banned for three decades. Surface water
contamination would remain only if DDTs are continuously introduced through atmospheric
deposition, stream runoff, and non point source inputs of surrounding soils and sediment
from both in and adjacent to the water body. A contribution of DDTs from atmospheric
deposition is not likely to account for a particular site-specific contamination within the 18-
mile stretch. The 10-fold increases of bioavailable DDTs in surface water at River Mile 7
West, as demonstrated in Figure 2.2, indicated the upstream sources were not as significant
as the local source at River Mile 7 West. Our findings (Figure 2.2) combined with lack of
organochiorine insecticides, including p,p'-DDE detected in the filtered water samples from
the Willamette River tributaries by Anderson et al. (38) suggest the tributary influences on
the bioavailable DDT distributions in the Lower Willamette River are probably small. Data
from Figure 2.2 further reveals that the ability of stream flow to transport bioavailable DDT
and its metabolites during high flow periods in fall is insignificant. These findings indicate
that sources upstream of the harbor are negligible for bioavailable DDTs.
38
-J
-J
0) 1400
0.
0
0
0.
DOTs
0 1200
0
0
1000
a)
C)
800 -
0
0
600 -
a)
800
0
C
0
600
0
400
Ca
200
<a
>
200
>
<a
0
<a
0
.0
1200
1000
400
.0
1400
0
0
:3
0.
-
300
300
p,p- DOT
250
C
200 C
C
150 -
200 150 -
0
0
o 100 -
100 -
.0
<a
p,p- DDT
250
a)
0
0
,ck
.6;
:3
50 -
>
<a
50-
00
0
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<a
0
.6
0.
çi;5
300
p,p- DDE
250 C
0.
200 C
0
a)
0
0
150 -
0
0
100-
.0
50>
00
(a
.0
+± +
50
<a
rir1r
>
00
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.6
p,p- DDD
1000
C
0
5
\1
\'Ô
p,p- ODD
800 600 -
C-)
400
C)
400
:3
.9
200
0
\
C)
.0
.0
-6;
800
0 600
C
0
0
>
<a
0
\?;
1
a)
C)
150-
C) 100
0.
C
200 -
.0
o,1206'
1000
p,p- DDE
250
%-
",
>
<a
0
.0
0
ee\1
Figure 2.2 Average concentrations of bioavailable DDTs in surface water at the lower
Willamette River at Portland Harbor, Oregon, using passive sampling device (n=186).
Passive sampling devices were deployed for 7-21 days during the periods of low flow in
summer, and high flow in fall of 2001-2004.
39
The bioavailable DDT concentrations at River Mile 7 West increased significantly
during low-flow in summer sampling events, indicating a source of DDT in this area may be
important. A former DDT manufacturing and handling facilities were approximately 1 mile
upstream of the sampling site at River Mile 7 West. The spatial distribution of bioavailable
DDT concentrations coincided with the DDT distributions found in sediment (15). Weston
et al. (15) reported surface sediment samples collected within 1 mile downstream of the
former DDT facilities contained DDT concentrations approximately 4- to 10-fold higher
than in the samples upstream or downstream. Historically discharged DDTs in sediment
could be recycling into the water column via the contaminated sediments (39). Contaminants
that are dissolved or associated with colloidal particles can exchange across sediment-water
interface by diffusive or advective processes (40, 41). Subsequently, the sediments as a
depositional reservoir for historically discharged contaminants could have become an
important source of contamination and continued to recycle deposited contaminants to the
overlying water column (42). The presence of bioavailable p, p'-DDT and its metabolites
presumably resulted from historically DDT-deposited sediments. The findings suggest that
historically contaminated sediments rather than external non-point sources have become the
dominant source of DDT contamination in Portland Harbor.
Dominance of bioavailable p, p'-DDD in surface water. The dominance of
bioavailable p, p'-DDD over bioavailable p, p'-DDE was observed. Figure 2.2 reveals p, p'DDD is the most abundant bioavailable DDT derivatives followed by p, p'-DDE, and p, p'DDT. The average percentage contributions of p, p'-DDD, p, p'-DDE, and p, p'-DDT to
DDTs in the samples from eleven sampling sites in four years were 53 ± 14%, 35 ± 11%,
and 13 ± 6%, respectively. In general, the principal insecticidal ingredients of technical DDT
contained p,p'-DDT 72%, o, p'-DDT 20%, p,p'-DDD 3%, o, o'-DDT 0.5% and other 4.5%
(43). Both p, p'-DDD and p, p'-DDE existed as by-products in technical DDT and have been
formed by environmental degradation of DDT. The high contribution of p, p' -DDD and p, p' DDE in the bioavailable fraction suggested a large proportion of p, p'-DDT has been
transformed to p, p'-DDD and p, p'-DDE. It is noteworthy that p, p'-DDD was also marketed
as an insecticide in its own right, as well as, being a reductive metabolite of p, p'-DDT (43).
In addition to being a reductive metabolite of p, p' -DDT, a large proportion of p, p' -DDD
40
could therefore indicate a direct input of p, p'-DDD in this area. The results indicated p. p'DDD was the most bioavailable p. p'-homolog in surface waters of the lower Willamette
River
The large bioavailable concentrations of DDTs coincided with large DDD/ DDE
ratios (Figure 2.3). The ratio of DDDIDDE was highly variable between sites and sampling
periods. The DDDIDDE ratio at River Mile 7 West was highly variable, 6.6 ± 2.1 in summer,
and 2.8 ± 1.3 in fall. The large proportion of bioavailable p, p'-DDD and the large ratio of
bioavailable DDD/DDE in surface waters could be governed by water solubility and the
partition coefficients (log K0 and log K). Water solubility of p, p'-DDT, p. p'-DDD and
p,p'-DDE are 0.0055 mg/L, 0.02 mg/L, and 0.1 mg/L at 20-25 °C (44). However, the
bioavailable p. p'-DDT, p. p'-DDD, and p. p'-DDE concentrations in this study were
measured at the level much below the water solubility and therefore water solubility is
unlikely to be the cause of the observation. Log K; 5.7 for p,p'-DDT, 6.1 for p. p'-DDD.
6.0 for p. p'-DDE are similar, as well the sorption coefficients (log K); 6.3 for p. p'-DDT,
5.0 for p. p'-DDD, 4.7 for p. p'-DDE at 20-25 °C (32, 44) are not likely to account for the
observation seen. It is unlikely that the large proportion of bioavailable p. p'-DDD and large
ratios of bioavailable DDD/DDE are the results of differences in solubility or partitioning,
suggesting the large bioavailable p. p'-DDD concentrations may be influenced by other
factors.
10
0
6-
aa
aa 4a 2-
0
3?
o
0
3
0
o
VT
V
0
summer
faU
0
(5
w
o
v
0
0 8-
0
0
ill
0
0
V
0
0
0
0
0
V
Figure 2.3 Distributions of bioavailable p. p'-DDD: p. p'-DDE ratios in surface waters at the
Willamette River, Oregon during the periods of low flow in summer, and high flow in fall
from 2001 to 2004 (n=186).
41
The large ratio of DDD/DDE was previously observed in the Portland Harbor
sediments from River Mile 7-8 West (15). Zeng and Tran (42) showed evidence for a strong
tendency for organochiorines including DDTs, to move from sediment to overlying water.
The similarity of DDT profiles in the sediment (15) and the water bioavailable fraction
supports the possibility of the movement of bioavailable DDT and its metabolites to the water
column from historically contaminated sediments. The large ratio of DDD/DDE could also
indicate the potential for reductive dechlorination of DDTs to DDDs in sediments under
flooded, anaerobic conditions (45, 46). Under anaerobic conditions in sediments, DDT is
mainly metabolized to DDD by reductive dechlorination either by microbial degradation or
by chemical reaction while under aerobic condition, DDT is metabolized to DDE by
dehydrochlorination (47-49). It is possible that the lower Willamette River at Portland Harbor
which is a deep and slow moving river (15) has a potential condition for anaerobic reductive
dechlorination of DDT to DDD rather than to DDE. In general, p, p'-DDE tends to resist
further degradation as compared to p, p'-DDD (48, 49). However, Quensen et al. (50) found
that in anaerobic marine sediments, DDE was dechlorinated to DDMU (1-chloro-2,2-bis-(4'chlorophenyl)-ethylene) three orders of magnitude faster than the transformation of DDD to
DDMU. In addition to direct input of DDD, anaerobic reductive dechlorination of DDT to
DDD and possible persistence to further degradation of DDD under anaerobic condition in
sediments may all be responsible for the enrichment of bioavailable p,p' -DDD in Portland
Harbor. However, further investigations of dechlorination conditions in the harbor sediment
are warranted.
Evidence of seasonality in bioavailable DDT concentrations. Seasonal variations
of bioavailable DDTs at the lower Willamette River at Portland Harbor were observed.
Seasonal variation of bioavailable DDTs is site-specific. Seasonal variation of bioavailable
DDT concentrations was only statistically different at River Mile 7 West (p = 0.002, t-test)
(Figure 2.2). A 2-fold decrease of bioavailable DDTs during periods of high flow in fall was
measured at River Mile 7 West. The decrease in fall is due to a decrease of bioavailable p, p'-
DDD. In contrast, bioavailable p, p'-DDT and p, p'-DDE did not decrease in fall. By contrast
to River Mile 7 West, bioavailable DDT concentrations at the other sites remained
unchanged between summer and fall.
42
30
water temperature
25 -
::
2015 10 -
=
5000k
30000
Co
.2
a)
>
river flow
20000 -
I
10000 -
e
=1=1
I
I
precipitation
4
3
2
0
0)
E
16
14
12
10
0
a
8
6
dissolved oxygen
0
§
0
0
4
50
p,p-DDT
400
300
200
100
iii
1 4OB
1050
700
350 0
500
400 =
300 200 100 -
p 'p -D D D
lk;I
p ,p-D D E
0
10
p,p-DDD: p,p -DDE ratio
8=
642-
w
0
O0
c'
c°'
e0
2.c0
00200
o
,Zc30
ec'° ee0 c'°
e
0
sam pling event
Figure 2.4 Estimated concentrations of bioavailable p, p'-DDT and its metabolites in surface
water at River Mile 7 West of the lower Willarnette River at Portland Harbor, Oregon in
relation to average water temperature, average river flow, total precipitation, total organic
carbon (TOC, black circle), and dissolved organic carbon (DOC, white circle) concentrations.
43
At River Mile 7 West, bioavailable DDT concentrations were significantly lower in
fall (p = 0.002, t-test), excluding October 2004 (Figure 2.4). Bioavailable p, p'-DDT, p, p'DDD, and p, p'-DDE concentrations in October 2004 were unusually high compared to the
concentrations measured in fall 2001 to 2003 and were treated as an outlier in this case, In
general, a significant decrease of bioavailable p, p'-DDD (p = 0.001, t-test) in fall appeared
to be a major driver of seasonality in bioavailable DDT concentrations. l3ioavailable p, p'DDT and p, p'-DDE were statistically unchanged between seasons (p = 0.58 for p, p'-DDT
andp = 0.50 for p, p'-DDE, t-test). The bioavailable p, p'-DDD concentration was positively
correlated with average water temperature (r2 = 0.62, p = 0.003), and negatively correlated
with average river flow (r2 = 0.39, p = 0.03) and total precipitation (r2 = 0.71, p <0.001)
(Figure 2.4). As dissolve oxygen concentration is a function of water temperature,
bioavailable p, p'-DDD was also negatively correlated with dissolved oxygen concentration
(r2 =
0.49, p = 0.0 16). Bioavailable p, p'-DDD concentration was not statistically correlated
to total organic carbon (TOC) and dissolved organic carbon (DOC) concentrations (Figure
2.4). The results suggest seasonal change in bioavailable p, p'-DDD concentrations is
potentially related to changes in temperature, river flow, andlor precipitation.
The average amount or load of bioavailable DDTs transported in surface water at the
lower Willamette River (River Mile 1-18) during the 4- year study in summer ranged from
1.1 g/d to 22 g/d for bioavailable DDTs; 0.11 g/d to 2.1 g/d for bioavailable p, p'-DDT;
0.61 gld to
18
g/d for bioavailable p,p'-DDD; and 0.36 gld to 2.7 g/d for bioavailable p,p'-
DDE. The average loads during fall were 2.6 g/d to 27 g/d for bioavailable
DDTs; 0.26 g/d
to 6.9 g/d for bioavailable p, p'-DDT; 0.86 g/d to 15 gld for bioavailable p, p'-DDD; and 1.3
g/d to 6 .0 g/d for bioavailable p, p'-DDE. The highest loads of bioavailable DDTs always
observed at River Mile 7 West during summer and fall. In general, the loads of bioavailable
p, p'-DDT and its metabolites were not significantly different between seasons (p > 0.05, ttest).
Daily average river flow and water temperature were used to evaluate the seasonality
of bioavailable p, p'-DDD concentrations and ratios of bioavailable DDD/DDE (Figure 2.4).
An increase of bioavailable p, p'-DDD concentrations occurred during the low flow in
summer with a maximum observed during extended dry periods. Simply, one might be
44
tempted to think dilution could account for the decrease in bioavailable p,p' -DDD
concentrations during fall sampling events when the river flow is large. However, if dilution
was the cause, dilution should decrease all analytes similarly; this was not what we found.
Both bioavailable p, p'-DDT and p, p'-DDE were found to have the same or higher
concentrations in fall as compared to summer. Also, the DDD/DDE ratio should not change if
dilution is a major cause. It appeared that physical-chemical processes governed by water
temperature and river flow variations alone could not explain the observed seasonal variation
in bioavailable p, p'-DDD. We hypothesize that the seasonal distribution of bioavailable p,p'DDD is governed by a combination of physical and biological factors that vary seasonally as
a function of temperature, flow velocities, and aquatic organism activities.
The occurrence of elevated bioavailable p,p'-DDD concentrations and bioavailable
DDD/DDE ratios in mid July to mid September coincided with elevated temperature.
Increase in water temperature could decrease the organic matter-water partition coefficient
(Kom) of contaminants (51). Schwarzenbach et al. (51) estimated increasing temperature by
10 °C could result in an estimated 30% decreased absorption coefficient for pyrene. The
effect of increasing temperature by approximately 10 °C in summer could result in an
increased dissolved fraction from the sediment-water exchange for DDTs. A 30% increase
in bioavailable DDTs release would result in elevated concentrations of DDTs in surface
water. However, it appeared that increase of DDTs release from the contaminated sediment
due to decreasing temperature-dependent absorption coefficients alone might not readily
explain the significant increase in DDD/DDE ratios observed in summer. This gap suggests
another influencing factor(s) that could contribute to the elevated concentrations of
bioavailable p. p'-DDD in summer.
Increased water temperature would also be expected to increase growth and activity
of benthic organism, microorganisms, eutrophication, and bitoturbation. Bioturbation by
burrowing organisms at the surface sediment can reintroduce sediment-borne chemicals to
the water column (52). Some aquatic plants can uptake and transform p, p'-DDT primarily to
p, p'-DDD (53). Increasing aquatic plant growth could lead to oxygen depletion as
microorganisms break down the dead tissues. The top layer of the sediment may be aerobic
or anaerobic depending on the condition of the water column above; however the sediments
45
quickly become anaerobic with increasing sediment depth (52). There was also declining
redox condition (p = 0.054, t-test) as water temperature and dissolved oxygen concentrations
changed in summer (Table 2.1), a contributing factor to enhance anaerobic condition in the
sediments. Anaerobic reductive condition is the dominant condition for reductive
dechlorination of p, p'-DDT top, p'-DDD by both microbial degradation and chemical
reaction (47-49). Slow moving surface waters during summer would enhance anaerobic
reductive degradation to
p, p'-DDD as Kale et al.(45) found p, p'-DDD was a major
metabolite of p, p'-DDT detected in sediment and overlying water under flooded condition.
Evaluated together, increasing formation and release of p, p'-DDD as result of increased
temperature, decreased dissolved oxygen concentration, and the condition favoring reductive
conditions in sediment during low flow in summer would contribute to an increase of
bioavailable p,p'-DDD and high ratio of DDD/DDE in surface water. As river flow and
precipitation increased in early fall, the formation and release of p, p'-DDD could be affected
by dilution process as suggested by relatively no change in DDDIDDE ratio. Decreasing ratio
of DDD/DDE in fall suggested seasonal influence on p, p'-DDD sources. As water
temperature decreased and river flow increased in fall, the condition suitable for reductive
dechlorination may have been altered resulting in decreased bioavailable p, p'-DDD
concentrations and change in bioavailable DDDIDDE ratios.
The above discussion contains speculation of the processes that highlights the lack of
understanding on how seasonal river conditions interact to yield the observed seasonal
variation in bioavailable p, p'-DDD and its relationship to bioavailable p, p'-DDE. Further
research is needed. Understanding the interaction of seasonal physico-chemical and
biological factors will afford confidence in using this knowledge to predict the long-term
seasonal effects of DDTs on aquatic community and increased confidence in extrapolating
information to other contaminated sites.
Potential risk of seasonal bioavailable DDTs on aquatic organisms. The present
study measured the bioavailable concentrations of DDTs in surface water which allowed a
direct assessment of the water quality in the Portland Harbor. Aquatic organisms can take up
large amount of DDTs over time from surrounding water where DDTs are present at very
46
low concentrations (54). It has been addressed that DDTs taken into aquatic organisms has
come from sunounding water while a large proportion of
DDTs in their body has come
from the food (54). To assess the potential impacts of seasonal distribution of DDTs on
aquatic organisms at the lower Willamette River, water concentration estimates were
compared to the national recommended water quality criteria (22) and the Oregon water
quality criteria (23) (Figure 2.6). Exceedances of the fresh water aquatic life criteria for
DDTs (1,000 pgJL for both national and Oregon criteria) were seasonally influenced and
limited to the samples from RM 7 West. The bioavailable concentrations of bioavailable
DDTs always exceeded the national and the Oregon criteria during low flow in summer.
During sunmier, the aquatic organisms at RM 7 West could have been exposed to a greater
amount ofDDTs, particularly p, p'-DDD, due not only to seasonally increased exposure
concentrations but also to increased uptake rate. As aquatic organisms are ectothemic, the
rate of metabolism undergoes an approximately 2-fold increase with every 10 °C rise in water
temperature (55). Cairns et al (55) suggested increased temperature could change respiratory
rate and membrane permeability and thereby leaded to more rapid uptake and hastened the
accumulation of a toxic dose. The effect of increasing temperature approximately by 10 °C in
summer could result in increased DDT bioconcentration from surrounding water. Water
concentrations determined in this study are the bioavailable fraction which has been known
as the uptaken form by aquatic organisms. Therefore, exceedance of DDT fresh water
aquatic life criteria, as well as, the potential to increase their ability to bioconcentrate DDTs
from surrounding water during warm weather can pose a potential risk for DDT chronic
toxicity to aquatic communities at River Mile 7 West.
47
1600
0
1400
0
S
1200
o
1000
O
National hesh
Water aquatic
life criteria and
Oregon criteria
0
A
a)
60003
0
.0
400 -
200-
t
o.
350
I0
ç
.0
8 0
in
in
150
ii
too
0
50
>
0
0
116*011
0
0
800
a
a
8
600
0
400
_iO
0
0 200
5hea0hcr5ena
pp-DDE
350
0
at
(it
Oregon human
0
-
400
0
1200
1000
a
National human
health water
quality criteria
450
p,p-DDD
1400
0
300
250
0. 200
at
0
1600
-
p,p-DDT
A
400
a
800
-
450
DDTs
Netional human
health water
quality csteria
.0
.5
.0
300
250
Netionel human
health water
qualrty criteria
A
£
200
S
t50
0
100
I
0
0
summer
A
fall
Figure 2.6 Spatial and seasonal distribution of bioavailable p, p'-DDT and its metabolite
water concentration estimates compared to the national recommendation water criteria (22)
and Oregon criteria (23) to protect aquatic organism from chronic exposure to DDTs and to
protect local fish consumers who consume fish and shellfish from the lower Willamette River
at Portland Harbor, Oregon.
Bioavailable concentrations of p. p'-DDT, p, p'-DDD, and p, p'-DDE were also
compared to the national and Oregon human health water quality criteria to estimate life-time
cancer risk for local fish consumers based on a 106 increased lifetime cancer risk (Figure
2.6). Exceedances of the human health water quality criteria for p. p'-DDT and its
metabolites were mostly observed at RM 7 West. Although no samples exceeded the national
criteria for p. p'-DDT (220 pgIL), all samples from RM 7 West exceeded the Oregon criteria
(24 pgIL). Exceedance of the national human health water quality criteria for p, p'-DDD (310
pgIL) was seasonally affected. Bioavailable concentrations of p. p'-DDD tended to exceed
the criteria during low flow in summer sampling events. Only a few samples exceeded the
criteria for p. p'-DDE (220 pg/L). Although, the human health water quality criteria is not
the direct approach for human health risk assessment for fish consumers but it is useful as a
screening approach for indicating potential areas of concern. According to the results in our
48
study, the potential adverse effects ofDDTs for local fish consumers were realized locally
at River Mile 7 West. This finding agreed with the bioaccumulation profiles of DDTs in
fish and human health risk estimates for DDTs (2 x 106 to 8 x 10-s) from consuming fish in
this area in our previous study (17, 18). The excellent agreement between the present study
and our previous fish study confirmed passive sampling devices can be used as a surrogate to
study bioavailable distribution of organic contaminants in contaminated water.
Distribution of bioavailable potychiorinated biphenyls (PCBs). Iii contrast to the
generally point source nature of DDT contamination, there were several former PCB using
facilities densely located on both sides of the river from RM 2-10.5 (56). These facilities
have been identified as potential sources of PCB contamination in the harbor. Elevated
concentrations of PCBs were detected in sediments and subsurface sediments from RM 3.5
to 9.5 (15). Dissolved PCBs or colloidal particle-associated PCBs in the sediment can
exchange across sediment-water interface by diffusive or advective processes, subsequently,
recycling historically deposited PCBs to the water column (40-42). In addition, the current
major sources of PCBs to urban rivers include direct urban runoff, urban community
wastewater discharge, sewage treatment works, and combined sewer flow discharges (5759). Considering the influence of multiple PCB local sources and upland land uses, the
sampling sites were then grouped into three locations; RM 1-8 (industrial area including most
of Portland Harbor superfund site), RM 12-13 (urban area) and RM 15-18 (residential area).
The spatial pattern of bioavailable PCB concentrations in water coincided with the
historically spatial PCB sediment distribution. A spatial pattern of bioavailable PCB
concentrations was observed in summer and fall (Figure 2.7). Bioavailable concentrations of
PCBs ranged from below detection limits (0.69-54 pg/L depending on congeners) to 410
pg/L at the eleven sampling sites from River Mile 1-18 during the four-year study with an
average concentration of 54 ± 55 pgIL. In general, higher bioavailable PCB concentrations
occurred in the industrial and urban areas from River Mile 1-13. Elevated concentrations of
bioavailable
PCBs usually reached a maximum at RM 3.5 East, the lower superfund site.
Average bioavailable concentrations of PCBs during low flow in summer ranged from 47 74 pg/L at the industrial area, from 26-33 pg/L at the urban area and from 12-15 pg/L at the
residential area. Average bioavailable concentrations of PCBs during high flow in fall
49
ranged from 37-170 pgfL at the industrial area, from 36-69 pgIL at the urban area and from
23-42 pg/L at the residential area.
i 320
-S
88
a.
150-
N
100-
500
0
i-i-I
lEi
-
Summer
Fall
s
Figure 2.7 Averaged concentration estimates of bioavailable PCB (pgIL) in water at the
Willamette River, Oregon according to river season (low flow, low precipitation in summer
and high flow, high precipitation in fall) in 2001 to 2004. The error bars denote 1 SD.
The bioavailable concentrations of PCBs in the lower Willamette River were
generally comparable with or lower than the dissolved concentrations determined in other
large water bodies in US including San Diego Bay (11 - 330 pg/L based on 27 PCB
congeners) (60), Lake Superior (90 ±10 pg/L based on 25 PCB congeners) (61), Lake
Michigan (340 -1700 pg/L based on 85 PCB congeners) (62), the Susquehanna River,
Maryland (500 -5300 pg/L based on 85 individual congeners) (10), and much lower than
those in some river systems around the world such as Minjiang River, China (200,000 2,500,000 pg/L based on 21 PCB congeners) (36). It is noted that comparison between PCR
contamination at the lower Willamette River and the other rivers did not account for the
variations from sampling technique used, the techniques used to extract the operationallydefined dissolved phase and numbers of congeners analyzed. Other techniques probably
overestimate the bioavailable concentrations.
50
Seasonal changes in bioavailable PCBs distributions. Bioavailable concentrations
of PCBs showed a discernible seasonal pattern at almost every sampling site (Figure 2.7). A
two-fold increase in bioavailable PCB concentrations was observed during the high flow in
fall, with the residential site (RM 15-18) statistically significant (p = 0.003, t-test). The
average daily amounts or loads of bioavailable PCBs transported in surface water at the
lower Willamette River also showed significant seasonal differences. Average of bioavailable
PCB daily loads in surface waters were significantly higher in fall; industrial area (p
0.002, t-test), urban area (p = 0.043, t-test), and residential area (p = 0,001, t-test). The
average of bioavailable PCB daily loads at the industrial area (River Mile 1-8) during high
flow in fall was 3.4 g/d, compared to 1.2 g/d during low flow in summer. At the urban area
(River Mile 12-13) and residential area (River Mile 15-18), the average of bioavailable PCB
daily loads during high flow in fall was 2.56 g/d and 1.46 g/d, compared to 0.62 g/d and 0.28
g/d during low flow in summer. In spite of the dilution effect, bioavailable water PCB
concentrations were larger during high flow in fall than during low flow in summer.
Bioavailable PCB composition in surface water. The average percent congener
distributions of bioavailable PCBs are shown in Figure 2.8. PCB 153 and PCB 138 (hexa-CB
homolog) were the most frequently detected bioavailable congeners with 85% and 73%
frequency, respectively. PCB 49 (tetra-CB) was the most abundant bioavailable congeners
followed by PCB 52 (tetra-CB) and PCB 153 (hexa-CB) as the second most abundant
bioavailable congeners detected. PCB 166 and two of the co-planar, dioxin-like congeners,
PCB 77 and PCB 126 were below the detection limits in all samples.
51
0
°
60
60
50
50
40
40
30
0
20
O
10
0
N-)('4QrC)
N-N
0
a
U)
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00
10
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N- 0 C)CJOON- N-
60
60
50
50
40
40
30
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o
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C
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U)
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a
20
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o 20
0
30
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60
50
40
30
o0 20
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a
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N0CCO(Da)OOCC N-C)
congener no.
N-0O)C'JO0 N- N-C)CC
N-N-
00
00CC N-C)
congener no.
Figure 2.8 Average percent contributions of PCB congeners in surface water at the lower
Willamette River during the periods of low flow in summer and high flow in fall in 2001 to
2004. The error bars denoted 1 SD.
Although bioavailable PCB concentrations and loads were found to have strong
spatial and seasonal variation, the PCB congener profiles did not. The congener profiles for
River Mile 1-8 and River Mile 12-13 were fairly uniform and no discernable seasonal
patterns were observed, Figure 2.8. The similarity of PCB congener profiles for the industrial
area at the superfund site (River Mile 1-8) and for the urban area upstream (River Mile 1213) suggests the local sources of PCBs at the superfund site are important enough to
significantly increase the concentrations of bioavailable PCBs in surface water but not to
substantially change composition relative to the surface water inputs from upstream.
52
The average percent congener distributions for River Mile 15-18 relative to the
average of the other sampling sites showed the bioavailable PCBs to be comprised of a
slightly different composition, with the distribution maximum shifted toward the hexa
homolog (PCB 138 and PCB 153) as compared to the other sampling sites, which favored the
tetra homologs (PCB 44, PCB 49 and PCB 52), Figure 2.8 and 2.9. However, the average
percent congener and homolog distributions at River Mile 15-18 became similar to those at
the other sampling sites in the periods of high flow in fall.
g 10
0)
C)
River Mile 1-8: summer
0.8-
River Mile 1-8: tall
0.4-
04
o
02E
a 02
E
g 00
C)
0
0.0
-CS
1.0
River Mile 12-13: summer
0)
, 08
C)
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0
o
E
0
-z
06
N
0.4 -
0)
o 0.2
E
0
10
River Mile 15-18: summer
0)
o
C)
0.8
a 02
I
0
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0
0
E
GSva GCB G5C5
River Mile 15-18: laO
0)
0
T
E
00
0 10
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06
04
0.4
0
0.2-
0
080.6 0.4 -
0200
,T
I']
Figure 2.9 Average ratios of PCB homolog to bioavailable PCBs (sum of 25 individual
PCB congeners) in surface water at the lower Willamette River during the periods of low
flow in summer and high flow in fall in 2001 to 2004. The error bars denoted 1 SD. See
detail of PCB homologs in text.
The present study suggests the sources of bioavailable PCBs in surface waters at the
lower Willamette were presumably dependent on seasons. Storm flow was especially
important. Both concentrations and daily loads of bioavailable PCBs increased during high
53
precipitation and high river flow, especially during episodic rainstorms in November of 2001
and October of 2004. The importance of high river flow enhancing PCB transport in surface
waters has been previously described (10). Foster et al. (10) demonstrated PCB sorption
coefficients (Kds) were decreased during storm flows and subsequently enhanced the
dissolved, or the "bioavailable" PCB concentrations in the surface waters. They indicated
the lower Kjs of PCBs during storm flows may be attributed to an increase in DOC, a change
in particle organic matter content, or shifts in PCB congener profiles to a greater extent of the
less chlorinated congeners. In the present study, DOC and TOC concentrations at the lower
Willamette River did not change seasonally over the 4 year-study period (Table 2). DOC and
TOC concentrations were not correlated with the bioavailable PCB concentrations. There was
no evidence of seasonal or river flow-related change in PCB congener or PCB homolog
profiles observed at River Mile 1-8 where an average 50% increase in bioavailable
PCB
concentrations was observed. In contrast, a shift in PCB congener and homolog compositions
toward the less chlorinated congeners was observed at River Mile 12-13 and River Mile 1518. High river velocities during storms can promote the transport of a relatively larger
fraction of course particles in particulate phase which have lower organic carbon contents
(i.e., changing organic matter content) and reduced PCB sorption(63). The results suggests
storm events (i.e., high river flow, high precipitation) may have disturbed the interaction
between PCBs and their associated organic matters resulting in remobilization of bioavailable
fraction from sediments or particulate matters.
Additional inputs during high flow in fall such as precipitation and stoi in water
runoff may have also contributed to elevated bioavailable PCB concentrations and PCB
composition changes during high flow in falls. Atmospheric transport including precipitation
is an important pathway for the transfer of PCBs to surface water as indicated in several
studies (12, 64, 65). Bremle and Larsson (12) reported precipitation was a dominant source of
PCBs in a Swedish river during high flow. The PCB congener and homolog profile in surface
water samples from the lower Willamette River were similar to that observed in rain samples
in other studies, which were dominated by tetra-chiorinated congeners, including PCB 52
(64, 65). The similarity of PCB homolog patterns in our study and those in rain samples by
others may suggest precipitation inputs as an additional potential source of PCBs into the
river system during high precipitation and further investigation is needed.
54
Urban storm waters and urban community wastewater discharges are another source
of PCB contamination in the surface waters (57 59). Rossi et al (57) reported urban storm
water was a major contribution to PCBs in Swiss urban water systems. In the New York/New
Jersey Harbor Estuary, USA, PCB concentrations in the influent were elevated during
storrns(59). Approximately, 3% of the annual PCB contribution from the wastewater
treatment plants were diverted and bypassed the wastewater treatment plants and discharged
through combined sewage overflow due to precipitation events(59). In the lower Willamette
River at Portland, combined sewer overflows to the Willamette River occur frequently (i.e.,
100 days or 50 events overflow in 2004), especially during periods of high precipitation
which usually start in mid October(66). The increase in bioavailable PCB concentrations and
loads which was coincident with high precipitation and sewer overflows (Table 2.1) may
suggest a significant contribution of PCBs from urban storm waters and urban community
wastewater discharges to the surface waters. The hypothesis that combined sewer overflows
and precipitation could be a major source of PCBs during high precipitation and high river
flow in the lower Willamette River warrants further investigation such as PCB fingerprints to
fully elucidate their contribution to PCB contamination. Further studies will be necessary to
estimate the impact of the internal sources (i.e., contaminated sediments) and other sources
(i.e., precipitation, runoffs, wastewater discharges) of PCBs and how much they contribute to
the PCB problem in the system in order to reduce the PCB load and risk to the aquatic
organism community.
PCBs-associated risks to aquatic community and human health. None of samples
exceeded the national and the Oregon fresh water aquatic life criteria for PCBs (14000
pgIL). In contrast, exceedances of the national (64 pg/L) and the Oregon human health water
quality criteria (79 pg/L) for fish consumers were often observed at the sampling sites within
the superfund site (River Mile 1-8) (see Figure 2.10) but no discernable seasonal pattern was
observed. Year-round exceeding the human health water quality criteria suggests consuming
fish and shellfish from this area may pose adverse health effect risk to recreational or
subsistence fishers based on a 106 increased lifetime cancer risk for PCBs. This suggestion
is consistent with risk estimates (9 x 106 to 5 x 10) for PCBs from consuming fish in this
area in our previous human health risk assessment study (17). The extent of exceedance
would have been greater if more PCB congeners were included for the measurement.
55
Nevertheless, this exceedance indicates that PCB contamination remains a significant
problem at the Portland Harbor superfund site.
450
A
400)
350 -
300A
a.
Q
>
250200
150-
A
A
0
O
A
0
A
100- £OA©*0
0iuhiiiii
50
A
Oregon human
health criteria
National human
health criteria
o
summer
A fall
Figure 2.10 Spatial and seasonal distribution of bioavailable PCB water concentration
estimates (sum of 25 individual PCB congeners) compared to the national recommendation
water criteria (22) and Oregon criteria (23) to protect local fish consumers who consume fish
and shellfish from the lower Willamette River at Portland Harbor, Oregon.
Seasonal changes in bioavailable dieldrin distribution. Bioavailable dieldrin was
detected at all sampling sites. Over the 4-year study period, the ranges of bioavailable
dieldrin concentrations in the mainstreams of River Mile 1-18 of the lower Willamette River
were from 10 to 140 pgIL. No discernable spatial pattern was observed for dieldrin. However,
river condition changes between low flow in summer and high flow in fall appeared to
influence the distribution of bioavailable dieldrin in the surface water. An increase in
bioavailable dieldrin concentrations was found at most sampling sites during periods of high
river flow, high precipitation in fall (p
0.046, 1-test), Figure 2.11. Bioavailable dieldrin
daily loads were also found to be higher in fall. The average daily loads of bioavailable
dieldrin ranged from to 1.5 to 3.8 gld during high flow, compared to 0.63 to 1.3 gld during
low flow. The increase in both bioavailable concentrations and loads of dieldrin were
56
coincident with high precipitation and high river flow. It is noted that the increases were
higher at the sampling sites upstream, particularly at RM 18 which was downstream of
Johnson Creek, an agricultural/urban creek. The seasonal pattern of bioavailable dieldrin
distribution illustrates the transport behavior for non-point source contaminants which are
widely dispersed and have no intentional seasonal application cycle such as with the current
use pesticides. Dieldrin was widely used in the Willamette basin before it was banned and
Johnson Creek has been found to be one of the most dieldrin contaminated areas in the
watershed (67). Elevated concentrations of bioavailable dieldrin during high flow and storm
events in fall suggests bioavailable dieldrin transport from contaminated site upstream
including erosional inputs to the river during precipitation runoff from land sources or
riverbed sediment (68).
0.
125
100-
D
-o
Ca
7550-
25-
>
0
-o
I 5NeSaSe5aS
I I'iru'
c5
11
S
summer
J
a-
150
a
125 -
ioo92
I
50--5
9225>
0
-o
A
ii
5NBNeaS
-
a
a
a
a
Oregon human
health criteria
A
- National human
health cntena
6
B
t:k:3
o
summer
A.fill
Figure 2.11 Seasonal distribution of bioavailable dieldrin in surface water at the lower
Willamette River at Portland Harbor, Oregon during the periods of low flow in summer and
high flow in fall of 2001 -2004. The top panel shows average concentration estimates of
bioavailable dieldrin while the bottom panel shows their distribution compared to the national
recommendation water criteria (22) and Oregon criteria (23) to protect local fish consumers
who consume fish and shellfish from this area.
57
Bioavailable dieldrin concentrations were compared to the national recommended
water quality criteria (22) and the Oregon water quality criteria (23). None of samples
exceeded the national (56000 pgIL) and the Oregon fresh water aquatic life criteria (1900
pgIL) for dieldrin. Exceedances of the national and the Oregon human health water quality
criteria for dieldrin were frequently observed in fall, particularly at the sampling sites
upstream. This finding is consistent with risk estimates (2 x 106 to 3 x l0-) for dieldriri from
consuming fish in this area in our previous human health risk assessment study (17).
Acknowledgment. This study was partially funded by the Society of Environmental
Toxicology and Chemistry (SETAC) Early Career for Applied Ecological Research Award
sponsored by the American Chemistry Council to K.A.A, the Oregon Department of
Environmental Quality for the McCormick & Baxter superfund site project 2002-2003, and
the Oregon Health Science University pilot project for the NIEHS/EPA Superfund Basic
Research Grant. The Royal Thai government scholarship to D.S. is acknowledged. We are
grateful for field assistance by R. Grove of USGS, Forest and Rangeland Ecosystem Science
Center, Corvallis, OR. We would like to express appreciation for field and laboratory
assistance of colleagues at Food Safety and Environmental Stewardship Program (FSES),
Department of Environmental and Molecular Toxicology, Oregon State University,
especially E. Johnson, G. Sower, and S. Visalli.
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63
CHAPTER 3
FIELD TRIAL OF TRIOLEIN-FREE LOW-DENSITY POLYETHYLENE
MEMBRANE AS AN IN SITU PASSIVE WATER SAMPLER
Sethajintanin, D', Johnson, E.R.
1
1,2
and Anderson, K.A
1,2
Department of Environmental and Molecular Toxicology
2
Food Safety and Environmental Stewardship Program,
Oregon State University, Corvallis, Oregon 97331
64
Abstract
Responding to a growing need for an inexpensive and simple time-integrative
sampling device for bioavailable hydrophobic toxic contaminants in water, a triolein-free low
density polyethylene membrane lay flat tubing (LFT) has been further developed. The LFT
sampler is similar to semipermeable membrane device (SPMD) based on the diffusion of
dissolvedlbioavailable target hydrophobic compounds through the aqueous boundary layer
and polyethylene membrane and the subsequent accumulation in the membrane and a neutral
lipid reservoir (i.e., triolein), mimicking uptake by living organisms. Unfortunately, the
interference stemming from the triolein impurities in SPMD has sometimes impeded the
analyses and some target analytes are sacrificed in the removal processes of triolein
impurities. Here, we demonstrate laboratory and field verification that the LFT without
triolein proved reliable and had the same benefits as SPMD, but was simpler, inexpensive
and lacked interference from the triolein impurities. A total of 370 LFTs and SPMDs were
deployed as a paired study at thirteen sampling sites in three different river conditions, 21day deployment, at the Portland Harbor superfund site, Oregon. LFT has shown the ability to
detect polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), and
organochiorine (OC) pesticides as efficiently as the SPMD. Its sampling efficiency suggested
the neutral lipid reservoir (triolein) present in SPMD was not generally necessary. Also,
biofouling was not a problem for its field application as compared to SPMD. This simpler
device tended to accumulate compounds with high log K0 faster than SPMD. LFT sampling
rates were estimated and modeled for 33 target analytes, including PAHs, PCBs, and
organochlorine pesticides. Approaching equilibrium appeared to be not a concern even at a
superfund site. The shortest duration estimated for compounds with log K0
4.4 to maintain
in linear uptake phase during LFT deployment is 24 days at water temperature 22 °C. A
method for spiking permeability/performance reference compounds as an indicator for the
effects of environmental conditions on the device uptake rate was achieved by using a simple
spiking method in a small volume of toluene. The successful determination of field derived
data illustrates the effectiveness and reliability of LFT for environmental monitoring.
65
Introduction
A wide range of passive sampling devices (PSDs) has been widely used in recent
decades for monitoring exposure and assessment of contaminants in water, air, and soils(111). Semipermeable membrane device (SPMD) (1), solid-phase microextraction (SPME)(2),
diffusive gradients in thin-films (DGT) (3), and other sampling foiiiiats with thin polymer
coatings (4, 8) are examples of passive sampling technique developed and used for
environmental assessment. The generally accepted major advantage of passive sampling
technique over the conventional approach is the ability to distinguish between freely
dissolved and bound molecules and focuses on the availability and activity rather than the
mere presence of chemicals (12). The freely dissolved fraction is environmentally relevant to
chemical bioavailability, toxicity, mobility and degradation process(13, 14). Instead of
measuring the total concentration in a medium, the passive sampling technique measures the
concentration in a reference phase which can be brought into equilibrium with the
medium(12). The availability of a chemical is measured based on the chemical potential
which is logarithmically related to its fugacity and linearly related to its freely dissolved
concentration in a particular medium (12).
The semipermeable membrane device (SPMD) introduced by Huckins et al.(1) is a
passive sampling technique that has been demonstrated to linearly sequester a variety of
nonpolar and moderately polar organic contaminants (15, 16). SPMD has rapidly gained
wide acceptance and has become commonplace for integrative sampling of environmental
contaminants in water, air, and even soil (2, 5, 7). The device consists of low density
polyethylene lay flat tubing containing a thin film of a neutral lipid,
95% pure triolein
(1,2,3-tri{cis-9-octadecenoyl]glycerol) (15, 16). It has been proposed that SPMD mimics key
mechanisms of bioconcentration including diffusion through biomembranes and partitioning
between organism lipid and the surrounding medium (15, 16). Although SPMD provides
many attributes such as a chemical bioavailability and simplicity of sample deployment and
sample extraction, analysis of SPMD has sometimes been severely hampered by interferences
stemming from polyethylene oligomers and triolein impurities (17, 18). Size exclusion
chromatography can remove polyethylene oligomers and most of oleic acid and methyl oleate
(18). However small amounts of oleic acid and methyl oleate remaining after size exclusion
66
chromatography are analytically problematic (18). Additionally, oleic acid in SPMD
dialysates could contribute to false positive toxicity using Microtox assays (19). Petty et al
(15) suggested a potassium silicate column can effectively removed oleic acid, unfortunately
it can also remove target analytes (18). Gustayson et aT (17) introduced a normal phase
application of a disposable column containing a dual-zone restricted-access sorbent to
separate methyl oleate from polyaromatic hydrocarbons (PAHs); however this method failed
to separate methyl oleate from moderately polar to polar analytes(18). Lebo et al. (18)
demonstrated purification procedure for triolein destined for use in SPMD could greatly
reduce interferences caused by impurities in the triolein. Nonetheless the implementation of
these efforts to reduce interferences stemming from the triolein impurities would be
expensive and laborious and some contaminants of interest are often sacrificed.
In addition to triolein, the polyethylene membrane itself contained a significant
portion of the total amount of dissolved target analytes accumulated by an SPMD in a
'aboratory aquatic system (1). Booij et al. (20) revealed the equivalent efficiency of SPMD
and low density polyethylene membrane alone in sampling polychiorinated biphenyls
(PCBs), PAHs, and chlorobenzenes under controlled conditions, indicating the role of triolein
in the exchange kinetics was insignificant, particularly for compounds with log K0 > 6. The
importance of the polyethylene membrane as a solute reservoir in a three compartment model
(water, polyethylene and triolein) has been mentioned by Gale (21). Additionally, the
sampling rates of SPMD and the single layered polyethylene membrane sampler were not
significantly different for compounds with log K0 4-7.5 at three different temperatures (22).
Unlike the triolein impurities, analytical interferences from polyethylene membrane (i.e.,
polyethylene oligomers or polyethylene waxes) are readily removed by size exclusion
chromatography (18). Therefore preparation and sample extraction of triolein-free low
density polyethylene lay flat tubing (LFT) are less laborious and less expensive.
The triolein-free low density polyethylene membrane lay flat tubing (LFT) would be
an alternative passive sampling device for monitoring exposure and assessment of
contaminants. This simpler and less expensive sampling device would reduce the complexity
of SPMD kinetic modeling and sample extraction, but provide the same benefits. However,
there are some concerns for use of LFT. It was noted that the polyethylene membrane without
67
triolein appeared to be more subject to biofouling and it potentially reached equilibrium
faster than SPMD because of its smaller sorption capacity (20, 21). We suspected that LFT
would not reach equilibrium at ambient environmental concentrations of hydrophobic organic
contaminants, suggesting the applicability of this simplified device. Also, information on the
kinetic phase of chemical uptake during field deployment could be obtained by using
permeability/performance reference compounds (PRCs) as an in situ calibration approach
(20, 23). PRCs are analytical non-interfering compounds with moderate to relatively high
fugacity from PSDs, which are added to the PSD prior to membrane enclosure(23). Because
both the uptake and the dissipation of organic chemicals are controlled by the same molecular
processes, in situ dissipation rates of PRCs would allow for estimating in situ PSD uptake
rates (20, 23). For SPMD, triolein also served as a handy carrier for PRCs. A different
approach needs to be developed for a triolein-free polyethylene membrane. Booij et al. (24)
has developed spiking method based on equilibration of polyethylene membrane in 80/20
(v/v) methanol/water solution of PAHs and PCBs with log K0 3.9-7.7. However, variations
in both the amount and the evaporation rates of the solvent that stuck to the membrane were
sometimes problematic (24) and the membrane-solution partitioning coefficient was required.
A suitable spiking method is thus needed.
Although the feasibility of LFT as an alternative passive sampler in aquatic systems
has been mentioned in a few studies(20-22), its field application and demonstration were very
limited (25). Further study of LFT as an alternative approach for passive sampling technique
is worth the effort due to its comparable efficiency to SPMD and lack of interference from
the triolein impurities. Development of LFT in both theoretical and experimental work as
well as field study should be explored to promote a more complete understanding of its
sampling mechanism and its applicability in the field.
In this study we evaluated the use of LFT as an alternative device for monitoring
bioavailable hydrophobic organic contaminants in surface water and compared to to SPMD.
A method for spiking PRCs into LFT was developed and their recoveries were tested in the
laboratory under flowing water and in the field environment. LFT and SPMD were deployed
side by side as a paired study in a contaminated harbor site in the lower Willamette River at
Portland Harbor, Oregon. LFT sampling rates for selected polycyclic aromatic hydrocarbons
68
(PAHs), polychiorinated biphenyls (PCB s), and organochlorine pesticides were estimated.
Field derived data demonstrated the effectiveness and reliability of LFT for environmental
monitoring.
Materials and Methods
Passive Sampling Devices. Low density polyethylene membrane lay flat tubing
(LFT) (Barefoot®) was purchased from Brentwood Plastic, Inc (St. Louis, MO, USA). The
LFT was free of additives. The wall thickness of LFT was approximately 75-95 m. Standard
SPMDs were purchased from Environmental Sampling Technologies (EST, St. Joseph, MO).
A standard size SPMD consists of a 91-106cm segment of 2.5cm wide low density
polyethylene lay flat tubing having a wall thickness of 70-95 tm and a surface area of 450
cm2, that contains 1 mL of 95% pure triolein (1,2,3-tri[cis-9-octadecenoyl]glycerol) as a
thin film and has a total weight of 4.5 g (15, 16).
Chemicals and solvents. Standards of organochiorine pesticides (purities
and PAHs (purities
PCBs (purities
98.5%)
99%) were from Chem Service, Inc. (West Chester, PA). Standard
99%) were from AccuStandard (New Haven, CT). SPMDs were fortified
with PCB 82, and dibenz[a,h]anthracene for use as PRCs. List of target analytes is present in
Table 3.1. Certified reference material of PCB congeners and organochlorine pesticides in
cod liver oil (SRM 1588a) was purchased from the National Institute of Standards and
Technology (NIST, Gaithersburg, MD). SRM 1588a was used for method validity and
accuracy purposes for the deteiiiiination of PCBs and organochiorine pesticides in complex
lipophilic matrices such as triolein. All solvents used were pesticide or Optima® grade from
Fisher Scientific (Fairlawn, NJ).
69
Table 3.1 Selected physicochemical properties of target analytes
PAHs
(26, 27)
chemical
MW
naphthalene
acenaphthylene
acenaphthene
fluorene
phenanthrene
anthracene
fluoranthene
pyrene
benz[a] anthracene
chrysene
benzo[a]pyrene
benzo[b]fluoranthene
128
152
154
166
178
178
(NAP)
(ACY)
(ACE)
(FLO)
(PHE)
(ANT)
(FLA)
(PYR)
(BAA)
(CHR)
(BAP)
(BBF)
benzo [k}fluoranthene (BKF)
(BPL)
benzo[g,h,i]perylene
indeno[ 1 ,2,3-c,d]pyrene (IPY)
dibenz[a,h] anthracen&' (DBA)
OC
p, p'-DDT
pesticides p ,p'-DDD
(28, 29) p, p'-DDE
PCBs
(30, 3])
dieldrin
methoxychiora
endrin'
- di-CBs
- tn-CBs
- tetra-CBs
PCB 8'
PCB 37
PCB 44
202
202
228
228
252
252
252
276
276
278
355
320
318
381
346
381
223
256
290
290
290
290
290
290
324
324
324
324
324
324
324
324
358
358
358
358
358
358
392
392
392
392
392
log
K0
3.4
4.1
3.9
4.2
4.6
4.5
5.2
5.2
5.6
5.9
6.5
6.1
6.8
7.1
6.6
6.5
5.7
6.1
6.0
3.5
4.2
5.5
5.1
5.9
6.0
minimal box
dimension (A)
length breadth depth
molecular
volume
(As)
8.9
8.8
7.2
8.4
3.1
3.1
126.9
8.8
11.1
11.5
11.7
10.7
11.4
13.7
13.6
13.6
13.6
13.3
11.5
13.2
15.6
13.1
8.1
3.2
7.2
7.7
7.2
9.0
9.5
3.1
3.1
3.1
3.1
3.1
3.1
148.8
160.4
169.5
170.3
187.7
186
13.0
13.5
10.3
13.4
10.2
9.4
7.7
8.9
9.3
9.1
10.2
10.0
9.3
8.7
9.5
8.6
8.9
11.0
4.4
8.8
8.8
3.1
4.5
3.1
3.1
3.1
3.1
212.9
212.2
228.6
230.3
231.1
244.3
255.4
8.2
7.2
5.6
7.7
6.6
234.9
259.1
PCB 49
6.1
262.8
PCB 52
6.1
11.4
7.8
5.6
262.8
PCB 60
6.3
265.2
PCB 74
6.7
4.8
13.9
7.8
PCB 77
6.5
267.6
PCB 82a
- penta-CBs
6.1
PCB 87
6.5
272.4
PCB 99
6.6
PCB 101
6.4
12.6
5.6
276.1
7.8
PCB 105
6.0
PCB 114
6.7
PCB 118
7.1
PCB 126
6.9
- hexa-CBs
PCB 128
7.0
282.4
PCB 138
13.9
7.8
5.6
6.7
PCB 153
6.9
13.9
7.8
5.6
289.4
PCB 156
7.2
PCB 166
7.0
PCB 169
7.6
265.2
- hepta-CBs
PCB 170
7.1
PCB 180
7.2
PCB 183
7.2
13.9
8.8
5.6
PCB 187
7.2
PCB 189
7.7
a used as permeability/performance reference compounds (PRCs) in passive sampling devices
molar
volume
(cm3/mol)
147.6
165.7
173
188
199
197
217
214
248
251
263
268.9
268.9
277
NA
300
261.3
246.4
243.1
226.4
247.3
268.2
268.2
268.2
268.2
268.2
289.1
289.1
289.1
289.1
289.1
310
310
310
310
310
330.9
330.9
70
Preparation of LFT. LFT was pre-cleaned by solvent extraction to remove
impurities. Briefly, the tubing was pre-extracted twice with dichioromethane (Optima®,
Fisher Scientific, Fairlawn, NJ) using a soxhlet extractor. After the second extraction, the
pre-solvent extracted LFTs were dried by pulling a vacuum through polyurethane foam
plugs. The apparatus was left under vacuum for approximately 48-72 hr at room temperature
or until dichioromethane was removed from LFT. After dried, LFT was stored in clean,
sealed paint cans, and frozen (-20°C).
Pre-extracted LFTs were heat-sealed at a distance of 2 cm from one end of which had
been folded to make a small loop. The fortification standard solution was pipetted into the
other end of the tube. The LFT used in the laboratory experiment were fortified with 100 tL
of 400 ng/mL of PCB 8, PCB 82, PCB 170 and endrin, 800 ng/mL of methoxychior, and 20
tg/mL of dibenz[a,h]anthracene in toluene. The LFT used in the field exposure were fortified
with 100 L of the mixture of PCB 82 and endrin (each at 200 ng/rnL) and
dibenz[a,h]anthracene (20 tg/mL) in toluene. These compounds were used as PRCs. Air was
removed by squeezing the solvent down the interior of the tube toward the seal by running
the tube through fingers (gloved hands). The remaining air was forced from the tube through
the open end and the tube was heat-sealed. The LFT constructed in the present study was 2.7
± 0.05 cm wide, 100 ± 0.22 cm long, with a mass of 5.5 ± 0.11 g and a surface area of 540
cm2. Fortified LFTs were individually mounted on stainless steel racks (EST, St. Joseph,
MO) and stored in cleaned paint cans which were tightly sealed and stored at -20°C until
deployment.
Evaluation of the spiking method of permeability/performance reference
compounds (PRCs) in LFT. In a pilot experiment, three fortified LFTs mounted on stainless
steel racks were placed in an aquarium glass tank (35 cm x 50 m x 30 cm) filled with flowing
tap water at flow rate 41 ± 7 mL/s and water temperature at 17 ± 1 °C in darkness to prevent
photodegradation of dibenz[a,h]anthracene. After 14 days, LFTs were sampled and cleaned
with gloved hands, then rinsed in iN HCI (for approximately 15 sec) (Trace metal grade,
Fisher Chemical, Fairlawn, NJ), 18 MQcm water, acetone (Pesticide grade, Fisher Scientific,
Fairlawn, NJ), and isopropanol (Pesticide grade, Fisher Scientific, Fairlawn, NJ),
respectively. LFTs were kept in clean glass amber jars and stored at -20 °C until analysis.
71
Unexposed fortified LFT, fortified LFT procedural blank, reagent blank, and fortified reagent
blank accompanied the exposed LFTs and were processed and analyzed exactly as the
exposed samples.
Demonstration of effectiveness and reliability of LFT for field deployment. LFTs
were tested at a field site in the lower Willamette River at Portland Harbor which is listed as
an impaired water body in the Federal National Priority List (NPL, so called a superfund site)
(32). The harbor sediments have been contaminated with PCBs, DDTs, PAHs, dioxinlfurans,
and heavy metals (33). Fish from this area were contaminated with DDTs and PCBs (34).
The Willamette River at Portland Harbor is deep, slow moving, and tidally influenced (33).
The harbor generally has a low sediment transport capacity (33). Surface water runoff is
determined by climate influence and varies according to season (33).
LFTs were deployed side by side with SPMDs at the lower Willamette River at
Portland Harbor from River Mile 1 to 18.5 which contained the Portland Harbor superfund
site (RM 3.5 to 9.5) and the McCormick and Baxter Creosoting Co. superfund site (RM 7
East). The eleven sampling sites were outside the main shipping channel and often near
stream outlets of various upstream land uses including industrial, urban/residential, and
undeveloped areas. Five individual PSDs were loaded in a flow-through stainless steel cage.
Duplicate cages of LFTs and SPMDs were submerged approximately 10 ft from the river
bottom and were suspended with an "anchor-cable-cage-cable-float" arrangement. PSDs
were deployed for 21 days. The average water temperature ranged from 9 to 22 °C. The five
PSDs were later combined for analysis. On retrieval, PSDs were cleaned by gently rubbing
with gloved hands in on-site water and the series of solvents described above. Cleaned PSDs
were kept in clean glass amber jars and transported on ice-packs. Samples were stored at 20°C until analysis.
Sample extraction and chemical analysis. PSD extraction and cleanup were based
on established protocols and only modified slightly as necessary (5, 15). Briefly, PSDs were
dialyzed in hexanes, 400 mL for 5 PSDs (Pesticide grade, Fisher Scientific, Fairlawn, NJ) for
18 hr, followed by a second dialysis with fresh hexanes for 6 hr. The combined dialysates
were concentrated by rotary evaporation and a TurboVap® LV evaporator (Zymark®,
72
Hopkinton, MA). The samples were cleaned and fractionated using gel permeation
chromatography (Waters® gel permeation chromatography cleanup system; Water® 515
HPLC pump, 717 Plus autosampler, Phenogel® column, 2487 dual X absorbance detector,
and fraction collector II) (Milford, MA) with dichloromethane (Opima®, Fisher Scientific,
Fairlawn, NJ) as the mobile phase at the flow rate of 5 mLlmin. Appropriate fractions were
determined by analyzing standards and fortified samples. The appropriate fraction (14-20
mm) was collected and split into two equal sub-fractions: 1) PCB and OC pesticides and 2)
PAHs. Both fractions were separately subjected to volume reduction using a TurboVap® LV
evaporator and solvent exchanged into iso-octane (Pesticide grade, Fisher Scientific,
Fairlawn, NJ) for PCB and OC fraction and acetonitrile (HPLC grade, Fisher Scientific,
Fairlawn, NJ) for PAH fraction with a final volume of 1 mL.
PCB congeners and OC pesticides were deteuiiined using GC-tECD (Agilent
Technologies 6890N Network GC system) (Palo Alto, CA) dual capillary columns (db-xlb
and db-17, J&W Scientific Inc., Agilent Technologies, Palo Alto, CA) /dual detectors.
Injector and detector temperature were at 250 °C, and 350 °C, respectively. The GC system
was operated with helium carrier gas and nitrogen makeup gas. The oven temperature
program was as follows: 100 °C (1 mm) and increased at 1.2 °Cmin1 to 265 °C (2 mm).
PAH detection and quantitation was performed on a Hewlett Packard HPLC series
1100 (Agilent Technologies, Palo Alto, CA) with dual detection by fluorescence and diode
array, both with multiple wavelengths. The fluorescence detector had an excitation
wavelength at 230 and emission wavelengths at 360, 410, and 460 nm; the diode array had
detection signals at 254, 242, and 230 nm. Only three compounds, fluorene, acenaphthylene,
and indenol (1,2,3-c,d) pyrene, were detected by diode array; the rest were detected with the
fluorescence detector. The column was a Phenomenex Luna C18 with 3-tm particle size
(Phenomenex, Torrance, CA). The instrument was run with a constant flow rate of 0.75
mL/min and a timed gradient for the acetonitrile/water eluent system. The time program ran
at 40% acetonitrile for 10 mm, was gradually ramped up to 70% acetonitrile for 15 mm, and
then ramped up to 90% acetonitrile for 19 mm. The program was held at 90% acetonitrile for
3 mm and then returned to 40%.
73
Field duplicates and field blanks (trip blank, field blanks, and field extraction blanks)
accompanying the deployed passive sampling devices during deployment, retrieval, and
transportation to the laboratory were included in every batch. These field blanks and
laboratory control blanks (i.e., procedural blanks, laboratory PSD controls, fortified samples,
and standard reference material) represented 30 to 40% of a sample set and were processed
and analyzed exactly as the deployed samples. The method detection limits (MDL) were
determined as three times the heights of coincident peaks observed for each compound in the
laboratory PSD control. For those analytes having no coincident peak, the MDLs were set at
a value equivalent to the lowest standard in the respective calibration curve.
None of the target analytes were identified in field blanks and laboratory control
blanks. The average percent recoveries of fortified samples were as follows: PAHs 70 ± 20%,
PCBs 66 ± 13%, p, p'-DDT 99 ± 20%, p, p'-DDD 85 ± 8%, p, p'-DDE 79 ± 7%, and dieldrin
75 ± 17%. The average percent recoveries in standard reference material were as follows:
PCBs 96 ± 24%, p, p'-DDT 99 ± 21%, p, p'-DDD 108 ±14%, p, p'-DDE 79 ± 11% and
dieldrin 114±27%.
Data analysis. Data interpretation was performed using SPSS® Version 10.0.1(SPSS
Inc., 1989-1999), Sigma Plot 2002 for Windows Version 8.0 (SPSS Inc., 1986-2001), and
Microsoft® Office Excel 2003 (Microsoft Corporation, 1985-2003). Standard descriptive
statistics, paired t-test, linear regression techniques were used. In the field exposure
experiment, the efficiency of LFT to sequester hydrophobic contaminants was evaluated. The
efficiency of two PSDs was analyzed by comparing amounts of contaminants taken up per
unit mass of LFT and SPMD using paired samples t-test. Relationships of LFT
concentrations, SPMD concentrations, and physico-chemical parameters for PAHs, PCBs,
and organochlorine pesticides were examined by linear regression approach.
Results and Discussion
Evaluation of the spiking method of permeability/performance reference
compounds (PRCs) in LFT. In the laboratory study with LFT, LFTs were spiked with
74
selected PAHs, PCBs, and organochiorine pesticides in a small volume of toluene (100 tL).
These compounds were used as PRCs (Table 3.2). Averaged recoveries of PRCs in
unexposed LFTs were
75% except only for PCB 8 (2, 4'-dichlorobiphenyls) (log K0 = 5.1)
which yielded an averaged recovery of 62% (Table 3.2). PCB 8, a two chlorine substituted
congener, has a relatively high vapor pressure (6.9 x 102 Pa) (30) compared to other target
contaminants. It is plausible that volatilization of PCB 8 during sample extraction and
analysis could contribute to its loss. In general, the percentage recoveries of unexposed LFT
procedural control samples
75% indicated the dissipation of spiked compounds during
sample preparation, storage and handling, and extraction was negligible. The spiked
compound integrity was maintained until analysis. In addition, a stability test of spiked LFTs
that were kept in closed amber jars at room temperature (22-25°C) for three weeks yielded an
average recovery rate of 89% ± 11%. No significant loss of spiked compounds in the stability
test suggested loss of sample integrity during transport or storage under 22-25°C would be
negligible.
Table 3.2 Percent recoveries of permeability/perfoj titance reference compounds using simple
spiking method in a small volume of toluene.
permeability/performance
reference compound (PRC)
PCB 8
(log
= 5.1)
PCB 82
(log
= 6.1)
PCB 170
7.1)
(log K0
endrin
5.5)
(log K0
methoxychior
(log K0 = 4.2)
dibenz Ia,hj anthracene
(log K0= 6.5)
a
=2
percent recovery (%)
exposure under
unexposed laboratory
flowing water (n=3)
control (n=9)
PRC
clearance rate
keprc (d')
26±8.1
62±11
0.06
67±2.5
75±9.1
0.008
86±4.0
87± 10
0.0008
98±7.1
110±20
0.008
53±16
114±15'
0.05
91±4.2
93±13a
0.002
75
According to PRC approach, measuring the PRC loss over the exposure period
provides an in situ clearance rate constant of PRC (keprc) (23),
keprc = in (CpsDO / CPSD) t'
(1)
where CPSDO is the initial concentration of the PRC and CPSD is the concentration of PRC
remaining in the PSD following exposure, and t is exposure time in days. Comparison of the
keprcfield derived from the field exposed PSD to the keprclab measured in calibration exposure
(keprcfield / keprclab) can serve as an indicator of differences in the exposure conditions or the
effect of environmental variables on PSD sampling (23).
In a two-week laboratory flowing water exposure study, keprclab for compounds with
log
5.5
were less than 0.008 d' (Table 3.2). This finding confirms that polyethylene
membrane without lipid reservoir (i.e., triolein) has the capacity to retain hydrophobic
organic compounds by diffusive process in the polymer (21). The simple spiking method of
PRCs in a small volume of toluene was effective and valuable for further development of
LFT application. The result also suggests spiking with a small volume of other non-aqueous
organic solvents such as iso-octane is applicable. This method is simple, inexpensive and
provides the same benefit of a permeability! performance reference compound approach.
Demonstration of effectiveness and reliability of LFT for field deployment. As
part of our ongoing project for evaluation of seasonal bioavailability of contaminants in
surface water at the lower Willamette River at Portland Harbor, Oregon (35), passive
sampling devices were deployed for a period of 21 days. LFTs and SPMDs were deployed
side by side as the paired study at thirteen sampling sites in three different conditions;
average water temperature 9 ± 1°C /average river flow 14000 ± 4800 ft3/s, average water
temperature 22 ± 1°C !average river flow 8300 ± 390 ft3/s, and average water temperature 22
± 0.3 °C /average river flow 10000 ± 1700 ft3/s. The total of 74 composite samples (each
sample was a composite of 5 PSDs) of LFT and SPMD were compared. PCB 82, endrin and
diben4a,hjanthracene were used as PRCs in both LFTs and SPMDs to account for the effects
of environmental conditions on the device uptake rate.
76
Evaluation of LFT following field deployment. The outer surface of the body of LFTs
and SPMDs, following each deployment period, was covered in a thin film of silt. It appeared
that the samplers deployed under condition of water temperature 22°C I river flow 8300 ft3/s
in summer had slightly more fouling as compared to the other two conditions. However, in
all cases the degrees of fouling on the exterior surface of LFTs and SPMDs which were
deployed for 21 days were not significantly noticeably different. This observation differs
from previous observations in which triolein-free SPMD was reported to be more subject to
biofouling than SPMD (20, 21). After 21-day deployment of each sampling event, the total of
185 LFTs were not observed to have more biofouling than SPMD. The membranes of LFTs
and SPMDs appeared to be free from biofouling and algae growth. Heavy biofouling was
reported to reduce the permeability of diffusive-limiting membrane of SPMDs, resulting in
lowering the sampling rate by as much as 30% for phenanthrene (log K0 = 4.6) (36).
Additionally, it was noticed that the membranes of LFIs after deployment were slightly more
rigid than the membrane of SPMDs. The lack of rigidity of triolein-containing SPMD is
plausibly due, in part, to the formation of a thin film of triolein derivatives or triolein
impurities on the membrane exterior surface which might affect the contaminant uptake
mechanism of SPMD.
Evaluation of the influence offleld condition on contaminant uptake kinetic of LFT.
Both uptake rate and clearance rate of hydrophobic contaminants in the passive sampler are
governed by the same molecular processes (21). It has been proposed that any change in the
uptake rate of contaminants to the passive sampler should be reflected by a change in the
clearance rate from the passive sampler (20, 23). The device uptake rates may change due to
changes in temperature, flow velocity of the surrounding water, and biofouling on the
membrane surface during field exposure (23). The use of PRCs as an independent measure
for the exchange kinetics between the passive samplers and water allows for device uptake
rate adjustment for these field variables (20, 23). The ratio of the clearance rate constant
(keprcfield) in the field and in the laboratory (keprclab) can serve as an indicator to differences in
the environmental conditions. In addition, the information on the kinetic phase of
contaminant uptake under field exposure can be obtained from the clearance of PRCs in the
field (20). It has been suggested that the exchange kinetics are under aqueous boundary layer
control for compounds with log K04.4-8.0 and under polyethylene membrane control for
77
compounds with log K0 < 4.4 (23). However, it has been proposed that the use of PRCs with
log K0 4.4-5.5 was also applicable to the target analytes under membrane control (23). Thus,
the range of physico-chemical properties of PRCs used in this study was representative of all
target analytes.
The PRC approach was used in both LFTs and SPMDs in the present study. Table 3.3
presents percent recoveries and clearance rates (keprcfield) of PRCs in LFTs and SPMDs which
were paired-deployed under two different conditions. The PRC comparison study was done
at 22 °C. Booij et al. (24) suggested complete dissipation of a PRC with log K0 of 5
indicating all analytes with similar and lower log K0 had attained equilibrium phase. In
contrast, no dissipation of a PRC with log K0 of 6 indicating all analytes with similar and
higher log K0 were in the linear uptake phase (24). Significant retention of PRCs with log
K0 of 5.5 to 6.5 in both LFTs and SPMDs (Table 3.3) suggested linear uptake phase for all
target analytes could be assumed. Small deviation of the PRC recovery rates within each
condition indicated insignificant variation from analyses or site-specific condition variation
among sampling sites. Contaminant clearance times by LFT and SPMD were similar. The
mean PRC clearance rate (keprcfield) in LFT and SPMD was not different (0.02 d1 for LET and
SPMD at water temperature 22 °C, river flow 8300 ft3/s; and 0.02 d' for LFT and 0.01 d' for
SPMD at water temperature 22 °C, river flow 10000 ft3/s). Similar clearance time indicated
for a 21-day field exposure for both LFT and SPMD were governed by the same exchange
kinetics.
PCB 82, endrin, and dibenz {a,h] anthracene clearance rates in the LFTs were not
different between the two conditions (Table 3.3A and 3.3B). In contrast, the clearance rates
for dibenz [a,h] anthracene in SPMDs were somewhat different between the two conditions.
This finding suggests the exchange kinetics controlling more hydrophobic compounds such
as dibenz {a,h] anthracene (log K0 = 6.5) in LFTs is more robust to the changes in
environmental condition than in SPMDs.
78
Table 3.3 Percent recoveries and clearance rates of permeability/performance reference
compounds in the field exposed polyethylene lay flat tubing (LFT) and semipermeable
membrane device (SPMD) under different field conditions.
Average water temperature 22°C, average river flow 8300 ft3/s,
percent recovery (%)
field sample
laboratory and field
(n131
control (n=7)
LFT
SPMD
LFT
SPMD
permeability/performan
ce reference compound
(PRC)
PCB 82
6.1)
(log K0
endrin
(log
5.1)
PRC clearance rate
kep (d1)
keprc.field/
keprclab
LFT
SPMD
LFT
62±2.2
50±3.0
81 ± 8.2
80 ± 5.9
0.01
0.02
1.25
41±4.9
64±4.9
93±24
80±10
0.04
0.01
5
92±7.2
94±4.2
0.004
0.03
2
dibenz{a,hJ anthracene
84 ± 6.2 52± 13
6.5)
(log K0
a each sample was a composite of 5 PSD
Average water temperature 22°C, average river flow 10000 ft3/s.
permeability/performance
reference compound (PRC)
PCB 82
(log K0 = 6.1)
endrin
5.1)
(log K0
dibenz[a,h] anthracene
(log K0= 6.5)
percent recovery (%)
field sample
laboratory and field
(n=12y
control (n=7)
LFT
SPMD
LFT
SPMD
PRC clearance rate
keprcfield/
keprc (d')
kepc4ab
LFT
SPMD
LFT
65±7.8
54±6.0
73 ± 3.4
85 ± 8.9
0.006
0.02
0.75
33±7.7
89± 11
87±4.7
106± 15
0.04
0.008
5
85±4.4
65±7.6
92±8.5
100±4.8
0.004
0.002
2
a each sample was a composite of 5 PSD
Clearance rate ratios of PRCs between field and laboratory exposure in LFTs were
not different either of the conditions tested (Table 3.3A and 3.3B). This suggested the
increase of river flow from 8300 ft3/s to 10000 ft3/s or 20% difference did not significantly
affect on the contaminant uptake kinetics of LETs. The similar clearance rates of PRCs from
Table 3.3A and 3.3B indicated the biofouling effect and river flow variation between the two
conditions were negligible.
Although data for PRCs were not available for the sampling event of water
temperature 9°C, a temperature effect can be expected (22, 27, 29, 37). The contaminant
79
uptake rate by polyethylene membrane is dependent on temperature in both aqueous
boundary phase control and membrane phase control (16). Temperature can affect molecular
diffusivity (38). Elevated temperatures result in more Brownian movement and elevated
temperature media are less densely packed so that diffusivity of chemicals through them is
facilitated. Evidence of the temperature effect on polyethylene membrane uptake rates has
been documented (22, 27, 29, 37). For compounds under aqueous boundary control (log K0
4.4) (22) , the effect of a 13°C temperature change (from 9°C to 22°C) on aqueous
diffusivity can be estimated from the ratio of diffusion coefficient in water (D) at 9°C and
22°C from the Stroke-Einstein relation and the equation by Hayduk and Laudie (38). A 1.5-
fold increase in D was computed for a 13°C increase in temperature (D @ 22°C! D @ 9°C
= 1.5). It is noted that this calculation could not apply to the membrane boundary layer
controls (i.e., polyethylene membrane). However, temperature increase in the chemical
diffusivity in polyethylene membrane can be expected as there is increased polymer chain
movement within the membrane due to an elevated temperature. Any temperature increase in
the aqueous diffusivity and the membrane diffusivity should cause a corresponding increase
in the uptake rate by LFT. Because contaminant partitioning and diffusion occurred at both
aqueous boundary phase and polyethylene membrane layer, the uptake rates for compound
with log K0
4.4 are expected to increase at least 1.5 fold when water temperature changes
from 9°C to 22°C.
Comparison of contaminant accumulation in LET and SPMD. The paired LFT and
SPMD field exposure study demonstrated that LFT accumulated PAHs, PCBs, and
organochiorine pesticides as effectively as SPMD (Figure 3.1). Linear correlation between
contaminants concentrations in LFT and in SPMD (amounts of contaminants accumulated
per mass of PSD) (ng/g) indicated both devices functioned similarly. The capacity of LFT
and SPMD to accumulate PAHs, PCBs, and organochlorine pesticides was approximately
equivalent as expected from their similar surface areas. Lack of triolein as an ultimate
reservoir in the device did not affect the capacity of LFT to accumulate hydrophobic organic
contaminants under realistic exposure conditions. It has been hypothesized that a
polyethylene membrane-only sampler reached equilibrium faster than triolein filled sampler
(i.e., SPMD) because of their smaller sorption capacity, making it a poor choice for
integrative long term monitoring (21, 22). Our study was conducted at a superfund site where
80
the river system has been contaminated with a wide range of contaminants. The result from
our study indicated that LFT did not reach equilibrium state during a 21-day field exposure at
a highly contaminated system. This finding indicated LET performed at least as well as
SPMD within the environmentally observed ranges of PAHs, PCBs, and organochiorine
pesticides.
Concentrations of contaminants accumulated in LFT and SPMD at each sampling site
for each deployment were statistically compared (a paired t-test, two-sided p-value
0.05
was considered significantly different). The mean concentrations for p,p'-DDT, p,p'-DDD,
p,p'-DDE, and PCBs (sum of 25 individual PCB congeners) in LFT were higher than in
SPMD in all three different conditions. The congeners with log K0 ranging from 6.0 to 7.0
were more concentrated in LEE than in SPMD. No statistical differences were observed
between the concentrations in LEE and in SPMD for the congeners with log K0 < 6.0 or>
7.0. The mean concentration of dieldrin, by contrast, was higher in the SPMD. No significant
difference was observed for the mean concentration for PAHs (sum of 15 priority pollutant
PAHs). However, the mean concentrations of three-ring PAHs with log K0 <4,5 were
higher in the SPMD. On the other hand, the mean concentrations of PAHs with log K0
6.0
were higher in LFT. No differences were observed between the concentrations in LEE and in
SPMD for PAHs with log K0 4.5-5.5.
81
4
V
V
.-0
01
50.8-
0
0
0.6
-5 0.4
ci)
0.2
r2=0.9331
= 0.7255
J) < 0.0001
p<O.0001
0.0
00
0.2
0.6
0.4
0.8
12
1.0
0
dieldrin in LFT (ng/g)
25
20
0 15
5
6
3.5
a)
.E. 3.0
0
V
0
2.5
0
10
C/) 2.0
-
C
C
0
0
4
4.0
0
C
Cl)
3
2
1
pp-DOT in LFT (nglg)
S
w 1.5
0
1.0
a-
-
=0.9488
p<O.000l
0.0
0
5
15
10
25
20
p,p-DDD in LFT (ng/g)
30
0
1
2
3
4
5
6
7
pp-ODE in LFT (ng/g)
3000
-2500
a)
2000
1500
C/)
.
1000 -
50::
0
2
4
6
FOBs in LFT (nglg)
8
10
0
500 1000 1500 2000 2500 3000
PAHs in LFT (ng/g)
water temperature 9°C, river flow 14000 ft3ls
o water temperature 22°C, river flow 8300 ft3/s
water temperature 22°C, river flow 10000 ft3/s
Figure 3.1 Relationship of contaminant concentrations in the triolein-free polyethylene lay
flat tubing (LFT) and in semipermeable membrane device (SPMD). Linear correlation
suggests both devices are governed by the same uptake model and function similarly. This
indicates LFT can accumulate the selected contaminants as effectively as SPMD regardless
of field variations.
82
Spatial distributions of contaminants accumulated in LFT were compared to those in
SPMD. Figure 3.2 is an example of three deployments during 2003 to 2004. This 21-day
exposure was taken during a period of water temperature 22 °C, river flow 8300 ft3/s in
summer of 2004. The spatial patterns for organochiorine pesticides and PAHs in
polyethylene lay flat tubing were identical to the patterns in SPMD. The spatial patterns for
PCBs in the two passive samplers were only slightly different at some sampling sites. This is
mostly likely due to SPMD PCB concentrations near detection limits. A small variation
between the PCB distributions in LFT and in SPMD at those sites is less significant
especially when one considers the close resemblance of contaminants at the other sites.
Compositions of PAHs and PCBs accumulated by LFT and SPMD from side by side field
deployment were also very similar (Figure 3.3). The field exposure demonstrated the
congener distributions and total concentrations were strongly correlated between the two
sampling devices.
The LFT/SPMD concentration ratio was independent of temperature and flow regime
in this study. The LFT/SPMD concentration ratio versus log K0 (Figure 3.4) shows that for
the forty-five contaminants tested, twenty-three were found to uptake in LFT faster than in
SPMD (below detection limit contaminants were excluded from the discussion). For
contaminants with log K0> 5.0, except PCB 37 and PCB 187, the LFT/SPMD concentration
ratio is
1. Only ten compounds, generally all with log K0
4.5, were found to have
LFT/SPMD concentration ratios < 1.0. This finding indicates the role of triolein is
insignificant for a compound with log K0
5. For a compound with less hydrophobicity,
triolein had more effect on contaminant accumulation. The effect of triolein on the amount
taken up was about a factor of two for a compound with log K0
4.5. In a laboratory flow
control study by Booij et al. (20) using four SPMDs without triolein, the ratios of amounts
taken up by SPMD without triolein / with triolein were equal for compounds with log K0>
6, and the effect of triolein on the uptake kinetics was as large as a factor of four for a
compound with log K0 = 4. Our field study results corroborated the laboratory exposure
results by Booij (20), indicating the overall effectiveness and reproducibility of LFT for
sampling hydrophobic contaminants.
83
0)
0)
dieldrin
25
c 25 -
-0-- p,p- DDE
-'- p,p-DDD
v--- p,p-DDT
10
20a. 15 ci)
10.
C
4C)
0
.2
5
.::
0-
0-
C
C)
C
8
b0
0) 10
£8
PCBs
C)
£ 8-
F-
0
C
(I)
U-
._i6
0
4
.
C
02
C)
CC
C)
Co
0
C.)
C
0
C
C)0
0
S
0)
3000
2500
-
PAHs
0
0
2000
ci
C
0
S 2500
0
2000
3000
0)
1500 -
0)1500
1000-
C 1000
.2
500-
500
0..
C)
0
b <D <
o
Figure 3.2 Comparison of spatial distributions of selected contaminants accumulated in
the triolein-free polyethylene lay flat tubing (LFT) and in semipermeable membrane
device (SPMD). LFT and SPMD were deployed side by side at the lower Willamette
River at Portland Harbor, Oregon for 21 days in summer of 2004. Duplicated samples
were deployed at River Mile 1 and River Mile 18.
20
LFT
PCBs = 5.61 ± 0.31 nglg
n=2, site = RM 1
22°C, 8300 ft3Is
0
0
0
10
84
60
I
50
LFT
PAHs = 523 ± 59 ng/g
40
n=2, site = RM 1
9°C, 14000 ft3/s
-1
30
ci,
0
0
20
10
1)
ci)
.20
SPMD
PCBs = 4.12 ± 0.30 ng/g
n=2, site = RM 1
ci,
0
22°C 8300 ft3/s
10
0
60
SPMD
I< 40ci)
PAHs=618+210ng/g
50-
n=2, site = RM 1
9°C, 14000 ft3!s
a-
-1
30-
0
0
N C) C'JO
r- NC)- Lfl
OuJF<tI<iuJ)<
<OOJiz-i>-<I<QJQ-OaJ
C')(D CD C)OQC) N. C)
QOQQftQOQOOOOOOOCOOOOOOOO
OQOOO.
Figure 3.3 Percent composition of PCBs and PAHs (average ± lsd) in the triolein-free
polyethylene lay flat tubing (LFT) and semipermeable membrane device (SPMD) which
were paired-deployed at the lower Willamette River at Portland Harbor, Oregon for 21 days.
Total concentrations and field condition are noted in each panel. See Table 1 for
abbreviations.
0.0
3
4
5
6
7
8
log K0
Figure 3.4 Average ratios of concentration of contaminants accumulated in the triolein-free
polyethylene lay flat tubing (LFT) and in semipermeable membrane device (SPMD) as a
function of octanol-water partitioning coefficient (log K0). See table 3.1 for abbreviation.
85
Estimation of LET contaminant sampling rates. The present study demonstrates LFT
is as efficient in sampling hydrophobic organic contaminants in water as is SPMD. The
efficiency and reliability of LFT suggest the neutral lipid reservoir (i.e., triolein) is not
always necessary. The LFT passive sampling device is theoretically less complex than
SPMD. LFT can be modeled as a two compartment system while SPMD is a more
complicated three-compartment system (21) Although less complex, the LFT passive
sampling device maintains significant capacity to sample waterborne contaminants in a
polluted eco-system. However, field application of LFT limited due to the lack of daily
sampling rates for contaminants. The contaminant sampling rates allow back-calculation of
aqueous contaminant concentrations. The input to the lack of established sampling rates for a
wide array of contaminants is necessary to provide assessment to water quality standard, as
well as temporal and spatial comparison.
The results in the present study, as well as, those by others (21, 22) indicate LFT or
polyethylene membrane alone share the same contaminant uptake mechanisms with SPMD.
Dissolved hydrophobic contaminants in water are transported by diffusion in the bulk
aqueous phase to the aqueous diffusion film, then diffusion through the aqueous film and
partition into the polyethylene membrane (21). Booij et aL (22) observed the difference
between polyethylene membrane-water partitioning coefficients and SPMD-water
partitioning coefficients from fifteen samples at three different temperatures were less than
0.6 log unit in the 4< log K0 <6, suggesting the significant role of polyethylene membrane
in contaminant uptake. There was no evidence of significant differences observed between
sampling rates of SPMD and single-layered polyethylene membrane sampler in their study
(22). The percent recoveries and clearance rates of PRC indicated the linear uptake model for
LFT samplers and SPMDs deployed in this study. Estimated water concentration (C) by
polyethylene containing passive sampling device (PSD) in the linear uptake model is
obtained from the following equation (16)
cw
=
CPSD MPSD R' t
-
(2)
86
where CPSD is the concentration of the contaminant in the PSD (i.e., SPMD, LFT), MPSD is the
mass of PSD in grams, R is the sampling rate in liters per day of PSD, and t is the exposure
time in days.
In the present study, LFT sampling rates for PAHs, PCBs, and organochiorine
pesticides were estimated as a function of SPMD sampling rates under the same field
conditions. When LFTs and SPMDs are pair-deployed, such as in this study, water
concentration and other variables are the same for the paired deployment, leaving an R as
the only unknown variable. Established SPMD sampling rates for PAHs, PCBs, and
organochiorine pesticides at multiple temperatures have been well documented (27, 29, 37,
39). LFT' sampling rates can be theoretically estimated from calibrated SPMD sampling rate.
RS.LFT
=
CLFT. MLFT. R r-SPMD CSPMD
MSPMD'
(3)
Table 3.4 presents the LFT sampling rate estimates (R) at 9 °C and 22 °C. The LFT
sampling rates were found to increase with increasing log K0 and exposure temperature
(Table 3.4 and Figure 3.5) as has been observed in SPMD (22). Large variation of LET
sampling rates was observed as log K0 and molecular size increased (Figure 3.5). Membrane
permeability limitation could be a factor contributing to this variation. Similar to
biomembrane cavities, the diameters of polyethylene membrane transient cavities range up to
9-10 A (15). This cavity size limitation impedes the diffusion of compounds with large
molecular size or particle-bound contaminants through the polyethylene membrane.
Contaminant molecules having at least two dimensions less than 10 A can readily diffuse
through the membrane cavities. Due to membrane cavity size limitation, reduction of LET
sampling rates for high K0 compounds with breadths
A, such as benz[a]anthracene and
benzo[k]fluoranthene, were observed (Table 1 and 4, and Figure 5). On the other hand, the
breadths of high K0 PCB molecules are < 9 A (Table 1) which allows them to diffuse
through the membrane cavities. Also, the biphenyl bond of PCBs allows molecular
conformation and rotation which may increase their membrane permeability. These
differences in compound characteristics may contribute to large variation of LFT' sampling
ratçs for high K0 compounds. Elevated temperatures may decrease the variation of LET
87
sampling rates for high K0 compound by increasing polymer chain movement within the
membrane, which can facilitate chemical transport through the membrane.
Table 3.4 Contaminant sampling rates for triolein-free polyethylene lay flat tubing (LFT)
estimated from field exposure to contaminated water at the lower Willamette River at
Portland Harbor, Oregon for 21 days. LFT sampling rates were estimated from established
SPMD sampling rates.
compou
nd class
PAils
compound
naphthalene
acenaphthylene
acenaphthene
fluorene
phenanthrene
anthracene
fluoranthene
pyrene
benzLa]anthracene
chrysene
benzo[a]pyrene
benzo[b]fluoranthene
benzo[k]fluoranthene
OC
p,p'-DDT
pesticides p,p'-DDD
p,p'-DDE
molar
volume
(cm fmol)
147.6
165.7
173
188
199
197
217
214
248
251
263
268.9
268.9
261.3
246.4
243.1
dieldrin
PCBs
-tn-CBs
PCB 37
PCB 44
PCB 49
PCB 52
PCB 74
247.3
268.2
268.2
268.2
-penta-CBs PCB 87
289.1
289.1
289.1
289.1
310
310
310
- tetra-CBs
PCB 101
PCB 105
PCB 118
-hexa-CBs PCB 138
PCB 153
PCB 156
- hepta-CBs PCB 170
PCB 180
log
K0.
3.4
4.1
sampling rate, Lid a
9C
n
1.3 ± 0.8
2.2 ± 0,8
11
39
b
4.2
4.6
4.5
5.2
5.2
5.6
3.4 ±
6.5
6.1
6.8
5.7
6.1
6.0
3.5
5.9
6.0
6.1
6.1
22 C
R
12
b
1.0
4.3 ± 2.0
3.5 ± 0.5
3.7 ± 0.4
4.5 ± 0.5
1.9 ± 0.3
12
12
11
12
12
2
b
b
b
b
b
b
2.4 ± 0.6
1.5 ± 0.5
2.3 ± 0.6
3.5 ± 0.8
4.2 ± 0.9
6.9 ± 1.1
8.3 ± 0.9
6,4 ± 1.3
4
13.7 ± 2.1
9.5 ± 2.6
5.8
1
b
b
7.1
4.1 ± 0.5
7.3 ± 1.4
6
4
3.5 ±
5
7.4 ±
1.3
1.0
6
b
b
b
b
8
22
21
10
12
7
4.5 ± 0.8
7.1 ± 4.7
6.3 ± 0.9
7
4.6 ± 1.4
7.7 ± 3.8
7.9 ± 2.6
8.7 ± 1.8
b
1.5
1.1
1.3
13
6
13
b
9.7 ±
6.0 ±
5.9 ±
b
12.6 ± 4.9
12.9 ± 6.4
3.5 ± 1.1
2.4 ± 0.3
1.6 ± 0.3
1.1 ± 0,1
6.7
6.5
6.4
6.0
7.1
b
11
12
12
12
12
7
12
3
6.7
6.9
7.2
fl
b
13.6 ± 3.0
11.5 ± 3.6
17.1 ± 3.3
16.8 ± 2.9
17.3 ± 3.9
11.5 ± 2.0
19.7 ± 3.0
16.6 ± 8.6
15.0 ± 4.2
12.4 ± 3.8
10.0 ± 3.1
16.5 ± 1.8
13.9 ± 4.7
7.4 ± 1.7
20
24
25
25
25
10
25
24
25
10
15
19
23
2
8
25
5
8
b
b
7.2
6
b
b
PCB 183
4
7.2
b
b
PCB 187
330.9
7.2
14
values are average sampling rates; number in parenthesis are I SD
a sampling rate estimates for 1 triolein-free polyethylene lay flat tubing (LFT) sampler with a 100 cm long
and 2.7 cm wide with a mass of 5.5 g and a surface area of 540 cm2
b
no value given due to concentration below detection limits
330.9
88
100
o
100
temperature 9 °C
temperature 22 °C
temperature 9 °C
temperature 22 °C
0
10
0
3
4
5
6
8
7
100 120 140 160 180 200 220 240 260 280 300
log K0
molecular volume (A3)
100
100
o
temperature 9°C
temperature 22°C
o
temperature 9°C
temperature 22 °C
Oo
0
00
S
U-
0
10
-1
S
S
100
150
200
250
300
molar volume (cm3/mole)
350
20
S
0
I
40
80
60
minimal molecular two-dimensions (A2)
Figure 3.5 Sampling rate estimates (R2L) of a 540 cm2 triolein-free polyethylene lay flat
tubing (LFT) as a function of log K0 ,molecular volume, molar volume, and minimal
molecular two-dimension.
From Figure 3.5, the initial sharp increase of sampling rates with increasing log K0
and molecular size is indicative of membrane-controlled uptake while the relative constancy
of sampling rates at the large log K0 and molecular or molar volume is indicative of aqueous
boundary layer-controlled uptake. For membrane-controlled uptake, R is proportional to the
product of the mass transfer coefficient for the polyethylene membrane (k1) and the
polyethylene membrane-water partition coefficient (K) (22). Increasing molecular size and
shape parameters can reduce membrane diffusivity (40). By contrast, since Kmw
5
hydrophobicity-related, it can be expected that increase in molecular weight, which is
proportional to molar volume and log K0, would increase Kmw. For aqueous boundary layer-
controlled uptake, the mass transfer coefficient for the aqueous boundary layer is a function
of the kinetic viscosity of the water, and the compound's aqueous diffusion coefficient (D),
89
which is negatively related to molecular size (40). The difference in LFT sampling rates
between compounds under aqueous boundary layer control can be preliminarily predicted
from water diffusion coefficient (D). However, it was found that aqueous diffusivity alone
cannot explain the difference in LFT sampling rates between compounds. For instance,
within the same PCB homolog group which has equal chlorine numbers substituted and equal
molar volume, LFT sampling rates for congeners with higher log K0 tended to have higher
LFT sampling rates. The result suggests although molecular size is a major factor controlling
aqueous diffusivity for a compound under the aqueous boundary layer-controlled uptake, the
hydrophobicity (log K0) that controls the chemical partitioning in the polyethylene
membrane maintains a significant role in contaminant uptake by the LFT sampler and cannot
be neglected.
According to the effect of aqueous diffusivity, a 1.5-fold increase in LFT sampling
rates for compounds under aqueous boundary layer control (log K0
4.4) was expected
when water temperatures changed from 9°C to 22°C (see section Evaluation of the influence
offield condition on contaminant uptake kinetic of LET). The estimated LFT sampling rates
for compounds with log K0 ranging from 4.4 to 7.2 rose an average of 3.4-fold with the 13
°C temperature increase. The difference between the predicted and field exposure values
indicated the temperature effect on aqueous diffusivity of a contaminant contributed 40% to
an increase in LFT sampling rate for a temperature difference of 13 °C. This suggested that
the other parameters involved in the uptake kinetic processes such as in the polyethylene
membrane boundary layer (i.e., membrane diffusivity, log K0, and molecular size) are also
significant contributors to an increase in LFT sampling rates for compounds under aqueous
boundary layer control (log K0
4.4).
Combining the effects of aqueous diffusivity, log K0, and molecular size on the LFT
sampling rates, the LFT sampling rates can be modeled using a linear regression model, see
Figure 3.6. Organochiorines and PAHs were separately modeled. Both models were
statistically significant (p <0.05), suggesting the LFT sampling rates can be predicted from
the product of the aqueous diffusivity, log K0, and the minimum molecular two-dimensions
of a contaminant. The fitting models for these two contaminant classes confirm the important
roles of chemical diffusion in both polyethylene membrane (log K0, and minimal 2-
90
dimension) and aqueous boundary layer (aqueous diffusivity, molar volume). The LFT
uptake rates for other PCB congeners or PAHs can possibly estimated using equations in
Figure 3.6.
20
y =37.99x-6.95
P
r2 = 0.79
101
138
15 - p <0.001
.PCP. 153
p,p4D
C152
10p,p
DD
PR
B
5-
p,pOT
pp-SaD:
PR
.PC153
,p4DE
P
F
ANT
A
0-
y =7.15x-0.71
r2 = 0.27
p =0.028
-5
00
D
0.2
0.4
0.6
0.8
10
1 O6.Cm2.S). Log K0Jminjmaj molecular 2-dimension (A2)
Figure 3.6 Sampling rate estimates of a 540 cm2 triolein-free polyethylene lay flat tubing
(LIT) sampler as a function of the product of aqueous diffusivity, log K0 and minimum
molecular two-dimension.
Another concern of using triolein-free polyethylene membrane as a passive sampling
device is its relatively small sorption capacity due to lack of triolein (21, 22), subsequently
the uptake phase would reach equilibrium during field deployment. In the present study, the
linear relationship between the amounts of contaminants accumulated in LIT and SPMD and
the results from PRC approach indicated both LET and SPMD were in the linear uptake
phase. In addition, times for the phases of polyethylene membrane sampler uptake can be
estimated from (16)
tj
= -in 0.5 K,w VPSD /R.
(4)
91
where tj,2 is the time required to accumulate 50% of the equilibrium concentration which
essentially represents the linear region of uptake, VPSD is the total volume of the PSD. Using
LFT' sampling rates in Table 3.4, the average deployment durations for compounds with 4.4
log K
7.7 to maintain in the linear uptake phase during LFT deployment are 2,250 days at
9 °C (range from 29 to 9,810 days) and 1,280 days at 22 °C (range from 24 to 6,860 days.
Evaluated together, our results confirm LFT sampler would not reach equilibrium during 21day exposure at realistic environmental concentrations even at a highly contaminated site
with a wide array of contaminants, such as Portland Harbor superfund site.
In summary, the triolein-free polyethylene lay flat tubing (LFT) showed the ability to
detect the selected hydrophobic contaminants as efficient as the SPMD. Its sampling
efficiency suggested the neutral lipid reservoir (triolein) present in SPMD was not always
necessary. Also, biofouling was not a problem for its field application as compared to SPMD.
This simpler device tended to accumulate compounds with high log IK faster than SPMD.
Approaching equilibrium appeared not be a concern at realistic environmental concentrations
for 21-day exposure. Spiking permeability/performance reference compounds can be
achieved by using simple spiking method in a small volume of toluene. The successful
determination of field derived data illustrated the effectiveness and reliability of the trioleinfree polyethylene lay flat tubing for environmental monitoring. Its application increases the
range of tools available to those involved in monitoring water quality. The method of choice
for environmental monitoring will depend on the contaminant nature and environmentally
relevant concentrations of contaminants as well as the objective of a study.
Acknowledgments. This study was partially funded by the Society of Environmental
Toxicology and Chemistry (SETAC) Early Career for Applied Ecological Research Award
sponsored by the American Chemistry Council to K.A.A. The Royal Thai government
scholarship to D.S. is acknowledged. We wish to thank R. Grove for his field assistance. We
would like to express appreciation for field and laboratory assistance by G. Sower, L. Quarles
and J. Basile.
92
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96
CHAPTER 4
ENVIRONMENTAL STRESSES AND FISH DEFORMITIES
IN THE WILLAMETTE RIVER:
COMPARISON OF PERSISTENT BIOACCUMULATIVE TOXICANTS
Doolalai Sethajintanin
Eugene R. Johnson
1,2,
and Kim A. Anderson
Department of Environmental and Molecular Toxicology
2
Food Safety and Environmental Stewardship Program,
Oregon State University, Corvallis, Oregon 97331
1,2
97
Abstract
In response to public concern related to the reports of a high incidence of skeletal
deformities in fish at the Willamette River, Oregon from River Mile 26.5-55, an area known
as Newberg Pool, a team of multidisciplinary scientists from Oregon State University
collaborated to identify the cause(s) of skeleton deformities associated with Willamette River
fish, with particular emphasis on the Newberg region. Our research group's effort was to
compare and contrast water chemical-physical conditions and the bioavailable fractions of
PCBs, DDTs, and dieldrin at the Newberg and Corvallis areas, where fish deformities were
significantly lower, and determine whether these factors were likely causes of the
deformities. In situ monitoring of river water quality coupled with in situ sampling and
analysis of bioavailable PCBs, DDTs, and dieldrin by semipermeable membrane device
(SPMD) were used. There were some differences in water quality parameters between the
Newberg and Corvallis sampling sites. However, they did not readily explain the difference
in deformity loads. Concentrations of bioavailable
PCBs,
DDTs, and dieldrin were
generally below 50 pg/L and the concentration differences observed between sites were very
small, with the mean concentration differences ranged from none to 27 pgIL. The results did
not provide compelling support for the hypothesis that PCBs, DDTs and dieldrin present in
surface water or differences in water quality parameters were a likely cause of the different
deformity loads observed at Newberg versus Corvallis.
98
Introduction
In response to public concern related to the reports of a high incidence of skeletal
deformities in fish at the Willamette River from River Mile 26.5-55 (an area known as
Newberg) (1-3), a team of multidisciplinary scientists from Oregon State University
collaborated to identify the cause(s) of skeleton deformities associated with Willamette River
fish, with particular emphasis on the Newberg region (4). The incidence skeleton deformities
in fish from the Newberg region had significantly greater deformity rates (56 %) than fish
from the upper Willamette River (i.e., 2-5 % at Corvallis), see location in Figure 4.1 (2). Precaudal deformity load in northern pikeminnow showed a spatial pattern with a significantly
higher incidence at Newberg area than the sampling sites at Newberg tributaries and the
upper Willamette River(3). The high frequency of skeletal defects at the Newberg area and
the gradual decline in the upstream and downstream direction suggested a local source as the
cause of skeleton defects in this region. The collaborative study consisted of three main
components as follows; investigation prevalence of skeleton deformities in juvenile fish from
the Willamette River focusing on Newberg (high prevalence) and Corvallis (low prevalence)
sites; comparison and contrast water physical and chemical conditions and distribution of
selected chemical contaminants at these sites; laboratory toxicity experiments with complex
chemical mixtures and other stressors from these sites. Together, these components provided
a weight of evidence based empirical approach to identify the likely cause of skeletal
deformities in Willamette fish. The final report has been published in Environmental Science
and Technology. Volume 39, No. 10, 2005, page 3495-3506, "Environmental stresses and
skeletal deformities infishfrom the Willamette River, Oregon" (4), see Appendix E.
Our research group's effort focused on the distribution of persistent bioaccumulative
toxicants in surface water. We compared water quality and potential for direct exposure to
these chemical contaminants at the Newberg sampling site, north and south side of the area at
River Mile 44 and 47, respectively, compared to the upper Willamette River sampling site at
Corvallis (River Mile 135) and determined whether these factors were likely causes of the
deformities. Inclusion of persistent bioaccumulative toxicants to be analyzed was based on
in-depth review of the peer-review literatures. A wide variety of chemical, physical, and
biological stressors have been associated with skeleton deformities in fish (5-10). This
99
chapter focuses on the distribution of chemical contaminants including polychlorinated
biphenyls (PCBs), DDTs (l,1-bis(4-chlorophenyl)-2,2,2-trichloroethane and its metabolites)
and dieldrin which have been reported to cause skeleton deformities by impairing
developmental processes and bone formation (6-8). Smith and Cole (6) found embryo
developing from eggs laid by adult winter flounder that were exposed to DDT showed a high
incidence of vertebral deformities caused by bone erosion and hemorrhaging at the vertebral
junctures. Olsson et al. (7) found offspring zebrafish following maternal exposure to certain
PCB congeners showed craniofacial and posterior malformation. Skeletal deformities have
also been linked to water quality problems, including low pH (5), low dissolved oxygen (11),
and elevated temperature (12).
The Willamette Bacin
N
D
major tributary enter5 river
Primary study sites
City lucaltuire for
eograptiic reference
Direction of flow
Figure 4.1 The Willamette Basin showing the general location and course of the Willamette
River and primary study locations.
The main purpose of this work was to compare and contrast water chemical-physical
conditions and the bioavailable fractions of PCBs, DDTs, and dieldrin at the Newberg and
Corvallis and determine whether these factors were likely causes of the deformities. In situ
100
monitoring of river water quality coupled with in situ sampling and analysis of bioavailable
PCBs, DDTs, and dieldrin by semipermeable membrane device (SPMD) were used. SPMD
consists of polyethylene lay flat tubing containing a thin film of a neutral lipid,
95% pure
triolein (1,2,3-tri[cis-9-octadecenoyl]glycerol) (13). It has been proposed that SPMD mimics
key mechanisms of bioconcentration including diffusing through biomembranes and
partitioning between organism lipid and the surrounding medium (14). During
spawning/early fish development (mid May through July 2002 and 2003), the in situ water
quality monitoring device (YSI 6920 SONDE; Yellow Springs, OH) and SPMD were
deployed to continuously collect a set of physical/chemical data. In this way episodic events
and other pulses of contaminants were captured. Temperature, dissolved oxygen, pH, specific
conductivity, oxidation reduction potential, NH-N,and NO3-N concentrations were
collected on an hourly basis during each 21-day sampling event.
Materials and Methods
Passive sampling device. Standard SPMDs were purchased from Environmental
Sampling Technologies (EST, St. Joseph, MO). A standard size SPMD consists of a 9 1-106
cm segment of 2.5 cm wide low density polyethylene lay flat tubing having a wall thickness
of 70-95 tm and a surface area of 450 cm2, that contains 1 mL of 95% pure triolein as a
thin film and has a total weight of 4.5 g (14, 15).
Chemicals and solvents. Standards of organochlorine pesticides (purities
98.5%)
were from Chem Service (West Chester, PA). Standard polychlorinated biphenyls (PCBs)
(purities
99%) were from AccuStandard (New Haven, CT). All solvents used were
pesticide or Optima® grade from Fisher Scientific (Fairlawn, NJ).
Sample collection. The Willamette River sampling sites were chosen to facilitate
investigation of spatial and seasonal bioavailable concentrations of organic contaminants at
Newberg and Corvallis during May to July 2002 and 2003 (Figure 4.1.). Two sampling sites
were located at Newberg; one on the south of the river (River Mile 47) and one a few miles
downriver on the north side of the river (River Mile 44). Two sampling sites were located at
101
Corvallis at River Mile 135. SPMDs and YSI 6920 Sonde (YSI, Yellow Springs, OH) were
deployed from May to July 2002 and 2003 to sample dissolved, bioavailable PCBs and
organochiorine pesticides and to collect water chemistry parameters, respectively. Three 21day sampling events were completed per year, one each in May, June, and July. The
sampling coincided with critical fish life stages during spawning and early development.
River depth and water chemistry parameters including temperature, dissolved oxygen, pH,
specific conductivity, oxidation reduction potential, NH-N,and NO3-N concentrations were
measured on an hourly basis by YSI 6920 Sonde.
Five individual SPMI)s were in a flow-through stainless steel cage. Each cage was
suspended 1 ft. from the river bottom with submerged with "anchor-cable-cage-cable-float"
arrangement. The five SPMDs were later composited for analysis. On retrieval, SPMDs were
cleaned by gently rubbing with gloved hands in on-site water, then rinsed in iN HCI
(approximately for 15 sec) (Trace metal grade, Fisher Chemical, Fairlawn, NJ), 18 MQ.cm
water, acetone (Pesticide grade, Fisher Scientific, Fairlawn, NJ), and isopropanol (Pesticide
grade, Fisher Scientific, Fairlawn, NJ), respectively. Cleaned SPMDs were kept in clean
glass amber jars and transported on ice-packs. Samples were stored at -20°C until analysis.
Sample extraction and chemical analysis. SPMD extraction and cleanup were
described in detail in Chapter 2 and 3. Briefly, SPMDs were extracted by hexanes dialyses
(Pesticide grade, Fisher Scientific, Fairlawn, NJ) in airtight amber glass jars. Sample volumes
were reduced using rotary evaporation and TurboVap® LV evaporator (Zymark®,
Hopkinton, MA). The samples were cleanup and fractionated using gel permeation
chromatography (Waters® gel permeation chromatography cleanup system; Water® 515
HPLC pump, 717 Plus autosarnpler, Phenogel® column, 2487 dual X absorbance detector,
and fraction collector II) (Milford, MA) with dichioromethane (Opima®, Fisher Scientific,
Fairlawn, NJ) as the mobile phase at the flow rate of 5 mLlmin. Appropriate fractions were
determined by analyzing standards and fortified samples. The fraction contained PCB and
organochlorine pesticides was subjected to volume reduction using TurboVap® LV
evaporator and solvent exchanged into iso-octane (Pesticide grade, Fisher Scientific,
Fairlawn, NJ) and were analyzed using GC-pECD (Agilent Technologies 6890N Network
102
GC system) (Palo Alto, CA) dual capillary columns (db-xlb and db-17, J&W Scientific Inc.,
Agilent Technologies, Palo Alto, CA) /dual detectors.
Quality control. Field duplicates and field blanks accompanying the deployed
passive sampling devices during deployment, retrieval, and transportation to the laboratory
were included in each sampling event. The Corvallis site was designated as a field duplicate
site. These field blanks and laboratory control blanks represented 30 to 40% of a sample set
and were processed and analyzed exactly as the deployed samples. None of the target
analytes were identified in field blanks and laboratory control blanks.
The percent recoveries of fortified samples were as follows: PCBs 57-110%, and
organochiorine pesticides 56-72%, relative percent difference between field duplicates was
46%. PCB 170 and methoxychlor were used as permeability/performance reference
compounds (PRCs), which were added to SPMD prior membrane enclosure (16). The use of
PRCs as an independent measure for the exchange kinetics between SPMDs and water allows
the device uptake rate adjustment for changes in temperature, flow velocity of the
surrounding water, and biofouling on the membrane surface during field exposure (16, 17).
The mean clearance rates of PCB 170 and methoxyclor indicated no significance loss during
SPMD deployment. Biofouling or algae growth on SPMDs was nil to minimal in this study.
No adjustment of sample concentrations for laboratory percent recoveries and percent loss in
field was taken.
Data analysis. The basic theory and mathematical models required for estimation of
analyte water concentrations from the concentrations in the SPMD have been described by
Huckins et al (15). Estimates of water concentrations (Cm) from SPMD concentrations were
calculated by the following equation (15),
C
= CSPMD MSPMD R
-1
where C SPMD is the concentration of the individual analyte in the SPMD, MSPMD is the mass
of SPMD in grams, R is the sampling rate of a standard 1-g triolein SPMD, and t is the time
103
in days. SPMD sampling rates (R) for PCBs and organochiorine pesticides at multiple
temperatures have been established (18-20).
Data interpretation was performed using SPSS® Version 10.0.1(SPSS Inc., 19891999), Sigma Plot 2002 for Windows Version 8.0 (SPSS Inc., 1986-2001), and Microsoft®
Office Excel 2003 (Microsoft Corporation, 1985-2003). Standard descriptive statistics and
the Mann-Whitney test (nonparametric two-independent-samples tests) were used to evaluate
differences between sampling sites and sampling year. Statistical analyses were considered
significant atp
0.05.
Results and Discussions
Water chemistry characterization. Temperature, dissolved oxygen, pH, oxidation
reduction potential, specific conductivity, NH4tN,and NO3-N concentrations were collected
hourly during all 21-day sampling events in May-July, 2002 and 2003 (Table 4.1). Discrete
sampling with 4-second interval was also measured during SPMD deployment and retrieval
and was reported when the 21-day data were unavailable. At each sampling site, some
parameters showed spatial and temporal variation while others did not.
The temperature patterns at Newberg and Corvallis sampling sites were similar for
both years and were generally 14 °C in May and rose to 20 °C by the end of the sampling
period. The average river temperature at Newberg sampling site was generally 1-2 °C higher
than at Corvallis. Diurnal temperature variation was similar at both sites (1-2 °C or less).
Dissolved oxygen probe tended to drift after about 10 days of deployment in some sampling
events. In that case the data after 10 days were excluded from the analysis. The dissolve
oxygen pattern was similar at both sites. A slight decrease in dissolved oxygen was seen from
May to July in both 2002 and 2003, as can be expected as water temperature increased.
104
Table 4.1 Spatial and temporal variations of water quality parameters at Newberg (River
Mile 44-47) versus Corvallis (River Mile 135) sampling sites on the Willamette River,
Oregon.
water quality parameter
temperature (°C)
year
2002
month
Newberg
Corvallis
May
14 ± 1.2
13 ± 0.93
June
16±1.3
16±1.3
July
19 ± 1.3
19 ± 1.5
15±0.Oa
2003
May
14± 1.7
June
17±1.1
16±1.3
July
20±2.0
19± 1.9
dissolved oxygen (mgJL)
2002
May
12 ± 0.49
11 ± 0.52
June
9.9 ± 0.61
9.2 ± 1.4
July
9.6 ± 0.35
9.5 ± 0.39
12±0.28a
2003
May
1o±o.o
June
11± 0.8
10±0.41
July
9.7±0.41
9.6±1.6
pH
2002
May
7.5 ± 0.06
7.6 ± 0.16
June
7.5±0.12
7.6±0.26
7.4 ± 0.01
July
7.3 ± 0.04
2003
7.4±0.0
7.4±0.12
May
June
7.4±0.16
7.7±0.4
7.4±0.1
July
7.2±0.10
260 ± 26b
370 ± 16b
oxidation-reduction
2002
May
120 ± 13b
340 26b
potential or ORE' (mV)
June
29017b
44033b
July
27040b
165 ±2.3 a
2003
May
38087b
29032b
June
44020b
39036b
July
specific conductivity
2002
May
0.063 ± 0.00 1
0.060 ± 0.002
(mS/cm)
June
0.057 ± 0.004
0.067 ± 0.004
July
0.078 ± 0.004
0.075 ± 0.003
2003
0.073 ± 0.002
0.064 ± 0.000 a
May
June
0.060 ± 0.006
0.063 ± 0.004
0.06 1 ± 0.002
July
0.087 ± 0.002
0.05 ± 0.01
2002
0.04 ± 0.01
May
NH-N (mg/L)
0.04 ± 0.01
0.09 ± 0.01
June
July
0.17±0.03
0.16±0.01
0.10±0.Oa
2003
0.04±0.01
May
June
0.10±0.02
0.07±0.02
July
0.03 ± 0.01
0.02 ± 0.00
2002
May
NA
NA
NO3-N (mgIL)
NA
June
NA
July
0.86 ± 0.05 a
1.17 ± 0.16 a
2003
May
1.1 ± or'
2.8 ± 0.30 a
June
NA
NA
July
0.36 ± 0.14 a
0.2 ± 0.0 a
a Continuous sampling data were not available. Discrete sampling data taken during SPMD deployment and
retrieval were reported.
b0 probe tended to drift after 7-10 days of deployment. Data after 7 data were excluded from the
analysis.
NA- data not available
105
Maximum pH range, usually in late May to mid June was 7.4 to 8.6 at Corvallis
sampling site, and 7.2 to 7.8 at Newberg sampling site. The daytime pH showed a strong
spatial difference, with the Corvallis sampling site often 1 + pH units higher than the
Newberg sampling site. By contrast, the night time pHs were similar at both sites. These
large diurnal pH changes were seen in both years. There were small decreases in pH from
2002 to 2003. Although some deformities in fish have been linked to pH effects such as
muscular and spinal deformities due to decalcification in white sucker held at pH 4.2 for over
4 weeks (5), we are unaware of any peer-reviewed literatures linking pH 7.2 to 8.6 conditions
to skeleton deformities in fish.
The oxidation reduction potential (ORP) probe tended to drift after 7-10 days of
deployment. Since all deployments were 21 days, data after 7 days were excluded from the
analysis. In 2002, the ORP was lower at the Newberg sampling sites as compared to the
Corvallis sampling site with the difference ranged from < 10% to a factor of 2. In contrast,
the ORP at Newberg was higher than Corvallis in 2003. There was some evidence that ORP
differed among years at the Newberg sampling sites. The ORP value is a direct reading of the
activity of oxidizing and reducing agents in the water as they correspond to oxidationreduction reactions. In general, there was no specific ORP pattern difference between
Newberg and Corvallis sampling sites although the Newberg waters were observed more
reducing than Corvallis waters in 2002. ORP is known to influence microbial growth, but it
was not clear whether the difference in ORP observed would make Newberg fish more
vulnerable to infection by microbial agents or more susceptible to deformities.
Specific conductivity was similar at the Newberg and Corvallis sampling sites for
both years. A seasonal increase in NH4tN concentrations was observed at both sites from
May to early July, with Corvallis generally having higher NH4-N than Newberg. The NO3N probe was not robust. In 2002, drift generally occurred within 24 hours of deployment. In
2003, the probe failed within a few hours of deployment. The limited data indicated that NO3
-N decreased from May to July, the concentrations were higher at the Newberg sampling
sites as compared to the Corvallis sampling sites. Evaluated together, water chemistry
parameters at both sites provided no compelling evidence to suggest that the differences in
106
these parameters were likely causes of the different fish deformity loads observed at
Newberg versus Corvallis.
Bioavailable polychiorinated biphenyls (PCBs). In the present study, PCB analysis
was based on a congener-specific approach; however, concentrations of all congeners were
quite low and were below detection limits (0.71-4.4 pgIL depending on congeners) in many
samples, so interpretation of results focused on PCB concentrations (sum of 24 congeners).
The bioavailable concentrations of PCBs were generally very low at all sites (Table 4.2).
During 2002 and 2003, biovailable PCB were generally greater at Newberg sampling sites
(Table 4.2). However, since most of the data were near or below detection limits, it was
difficult to draw any firm conclusions. Bioavailable concentrations of PCBs were
approximately 500-fold lower than the national and the Oregon fresh water aquatic life
criteria for PCBs (0.0 14 tgIL) (2], 22) and they did not readily explain the difference in
deformity load among sites.
Table 4.2 Mean concentrations (pg/L) of bioavailable organochlorines estimated from
concentrations accumulated in semipermeable membrane devices (SPMDs) exposed for 21
days at the Willamette River at Newberg and Corvallis (2 sampling sites per location) in
2002 and 2003
temporal
spatial distribution
chemical
2002
NP
CV
NP
CV
n=6
n=6
p-value
p-value
NP
CV
8.7±4.0
0.015
1.000
0.394
48 ± 11
36 ± 4.2
0.065
0.485
0.240
0.041
11±2.2
11±0.99
0.394
1.000
0.004
6.2±7.6
0.041
21±5.9
16±2.7
0.132
0.180
0.041
13 ± 19
0.18
15 ± 3.9
9.7 ± 1.6
0.026
0.180
1.000
8.1 ± 9.0
0.015
25 ± 5.9
14 ± 1.8
0.004
0.394
0.818
n=6
PCBsd
13±15
7.0±11
0.39
15±5.2
DDTs
49 ± 18
22 ± 28
0.18
p,pDDTc 10±5.2
p,pDDEc 16±5.3
p. pDDDd 23 ± 8.7
2.9±4.6
23 ± 6.8
p-value
2003
n=6
dieldrin"
distribution
asee chapter 1 for complete list of analyte. b significant difference between sites, both years.
significant difference between sites, 2002 only. significant difference between sites, 2003 only.
107
p, p'-DDT and its metabolites. The bioavailable
DDT (sum of p, p'-DDT, p, p'-
DDD and p. p'-DDE) concentrations were vary low at all sites in 2002 and 2003 (Table 4.2).
Bioavailable DDT concentrations were approximately 10-fold below the national and the
Oregon fresh water aquatic life criteria 0.001 pgIL (21, 22) which is the level generally
thought toxic to fish. The differences in bioavailable DDT between Newberg and Corvallis
sites in 2002 (p=O. 18) and in 2003 (p=O.O65) were not significant. In 2002, the bioavailable
DDT profile was dominated by p, p'-DDD, followed by p. p'-DDE and p. p'-DDT (Figure
4.2). In 2003, bioavailable p, p'-DDE dominated, followed by p, p'-DDD and p, p'-DDT.
This would be expected from older deposits and environmental degradation of p, p'-DDT to
its metabolites. Bioavailable p. p'-DDD and p. p'-DDE concentrations detected at Newberg
sampling sites in 2002 and 2003 were not significantly different (p=O.l8) (Table 4.1).
Bioavailable p. p'-DDE concentrations but not bioavailable p. p'-DDD concentrations at
Corvallis sampling sites increased significantly between 2002 and 2003 (p=0.04l for p, p'-
DDE and p=l for p, p'-DDD). The mean concentrations of bioavailable p. p'-DDT at
Newberg did not increase significantly between 2002 and 2003 (p=l), but the mean
concentrations of bioavailable p. p'-DDT detected at Corvallis increased significantly
(p=O.004). The cause of the increased p. p'-DDT concentration was not clear, but the results
suggest possible new inputs or sediment disruption remohilizing DDT. However, the
concentration differences observed were very small, so conclusions should be drawn
prudently.
80
-J
60
C
Newberg
Newberg
0
1 Corvallis
0 40C
0
0
p. p'-DDE
p. p'-DDD
p. p-DDT
Corvallis
C
0
0
2002
2003
Figure 4.2 The mean concentration distribution of bioavailable p, p'-DDT, p. p'-DDD and
p. p'-DDT at Newberg and Corvallis in 2002 and 2003
108
Dieldrin. Bioavailable dieldrin concentrations were significantly higher at Newberg
sampling sites as compared to Corvallis sampling sites (p=O.OlS for 2002 and p=0.004 for
2003) (Table 4.1). However, the bioavailable concentrations of dieldrin were very low and
there was no significant difference between years. The bioavailable dieldrin concentrations
detected were approximately 2000-fold below the national and the Oregon fresh water
aquatic life criteria, 0,056 tgIL and were well below those generally thought to be toxic to
fish (23). We are not aware of any reports linking picogram-per-liter concentrations of
dieldrin to skeletal deformities.
To draw causation of fish deformities at Newberg due to chemical stresses, we can
eliminate compounds that are absent, or if present, their concentrations do not differ from the
Corvallis sampling sites where fish deformities are relatively low. The results indicated the
difference between the presence or absence of bioavailable PCB congeners, p,p' - DDT and
its metabolites, and dieldrin detected at the Newberg and Corvallis sampling sites was
insignificant. For the compounds that were present there appeared to be little difference in
their water concentrations between the sites. The results did not provide compelling support
for the hypothesis that PCBs, DDTs and dieldrin present in surface water were a likely cause
of the different deformity loads observed at Newberg versus Corvallis. The results coincided
with the concentrations of these compounds found in fish ovarianloocyte and sediment
samples (4). Most organochiorine compounds were below detection limits in fish
ovarianloocyte and sediment samples and those that were detected were not significantly
different between sites. In contrast, the results from the other collaborative group found
metacercariae of a digenean trematode were directly associated with a large percentage of
deformities detected in Willamette River fish and similar deformities were reproduced in
laboratory fathead minnows exposed to cercariae extracted from Willamette River snail, see
detail in Appendix E. Therefore, the weight of evidence suggested that parasitic infection, not
chemical contaminants, was the primary cause of skeleton deformities observed in
Willamette River fish.
Acknowledgments. This part of the project was supported by a grant from the Oregon
Watershed Enhancement Board (no. 20 1-562). The Royal Thai government scholarship to
109
D.S. is acknowledged. We wish to thank R. Grove for his field assistance. We would like to
express appreciation for field assistance of J. Basile, O.Krissanakriangkrai and R. Adams.
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RC, Mogensen BB. Development of the permeability/performance reference compound
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111
CHAPTER 5
CONCLUSIONS
As part of an assessment of the bioavailability of a chemical contaminant, this
dissertation demonstrated the seasonal distribution of bioavailable organochiorine
contaminants in a river system and evaluated the potential environmental factors influencing
their bioavailability. The study was carried at the lower Willamette River at Portland Harbor,
Oregon where surface water runoff is determined by climate influence and varies according
to season. Bioavailable water concentrations of PCBs, DDTs, and dieldrin were determined
using polyethylene membrane containing passive sampling device, known as semipermeable
membrane device (SPMD). Our findings indicated that the influence of river seasonality on
the bioavailable distributions of organochlorine contaminants was compound- and sitespecific.
Seasonal variation of bioavailable DDTs was site-specific. A seasonally significant
increase of bioavailable DDT concentrations was observed during low flow in summer at
the sampling site just downstream of the former DDT production and handling facilities. The
large bioavailable concentrations of DDTs coincided with large DDDIDDE ratios. The ratio
of DDDIDDE was highly variable, 6.6 ± 2.1 in summer, and 2.8 ± 1.3 in fall. A significant
increase of bioavailable p. p'-DDD during low flow in summer was a major driver of
seasonality in bioavailable DDT concentrations. The linear regression analyses suggested
seasonal changes in bioavailable p, p'-DDD concentrations were potentially related to
changes in water temperature, river flow, and precipitation. Slow moving surface water,
declining redox condition, elevated water temperature and decreased oxygen concentration
during summer as observed in the present study would enhance anaerobic reductive
dechlorination of p, p'-DDT to p, p'-DDD by both microbial degradation and chemical
reaction in the sediment. In addition, the effect of increasing temperature in summer could
decrease the organic matter-water partition coefficient of contaminants, resulting in
112
increasing bioavailable DDTs release from the contaminated sediment. Evaluated together,
increasing formation and release of p, p' -DDD in sediment during low flow in summer would
contribute to the large increase of bioavailable p, p'-DDD and large ratio of DDD/DDE in
surface water. As water temperature decreased and river flow increased in fall, the condition
suitable for reductive dechlorination may have been altered, resulting in decreased
bioavailable p, p'-DDD concentrations and change in bioavailable DDDIDDE ratios.
The above discussion contains speculation of the processes that highlights the lack of
understanding on how seasonal river conditions interact to yield the observed seasonal
variation in bioavailable p, p'-DDD and its relationship to bioavailable p, p'-DDE. Further
research is needed such as confirmation of microbial communities responsible for reductive
dechlorination of p, p ' -DDT to p, p ' -DDD or reductive sediment condition and their role in
seasonal bioavailable p, p'-DDD distribution. Understanding the interaction of seasonal
physico-chemical and biological factors will afford confidence in using this knowledge to
predict the long-term seasonal effects of DDTs on aquatic community and increased
confidence in extrapolating information to other contaminated sites.
Bioavailable PCB concentrations were found to have strong spatial and seasonal
variation. Elevated concentrations of bioavailable PCBs usually reached a maximum at the
sampling sites within the industrial area. Both concentrations and daily loads of bioavailable
PCBs were significantly increased during high flow in fall, especially episodic rainstorms
and the discernable seasonal pattern was observed at almost every sampling site along the 18mile stretch of the study area. The results suggested the sources of bioavailable PCBs in
surface water at the lower Willamette River were presumably seasonally dependent. Storm
flow was especially important. Our results suggested storm events may have disturbed the
interaction between PCBs and their associated organic matter resulting in remobilization of
bioavailable fraction from sediments or particulate matter. In addition, the increase in
bioavailable PCB concentrations and daily loads which was coincident with high
precipitation and sewer overflows in fall suggested a significant contribution of PCBs from
precipitation input, urban storm water and urban community wastewater discharges to the
surface water.
113
The hypothesis that combined sewer overflows and precipitation could be a major
source of PCBs during high precipitation and high river flow in the lower Willamette River
warrants further investigation such as PCB fingerprinting to fully elucidate their contribution
to PCB contamination. Further studies will be necessary to estimate the impact of the internal
sources (i.e., contaminated sediments) and other sources (i.e., precipitation, runoffs,
wastewater discharges) of PCBs and how much they contribute to the PCB problem in the
system in order to reduce the PCB load and risk to the aquatic organism community.
Although no discernable spatial pattern was observed for dieldrin, an increase in
bioavailable dieldrin concentrations and daily loads was observed at most sampling sites
during high flow/high precipitation in fall. The seasonal pattern of bioavailable dieldrin
distribution illustrated the transport behavior for non-point source contaminants which were
widely dispersed and had no intentional seasonal application cycle such as with the current
use pesticides. Our results combined with the historical use of dieldrin in the watershed
suggested bioavailable dieldrin transport from contaminated site upstream including
erosional inputs to the river during precipitation runoff from land sources or riverbed
sediment.
To screen the potential impacts associated with seasonal changes of bioavailable
organochlorines on aquatic organisms, the bioavailable concentrations of DDTs, PCBs and
dieldrin were compared to the national recommended water quality criteria and the Oregon
water quality criteria. Seasonal exceedances of the criteria for DDTs were limited to only
the sampling site downstream of the former DDT production and handling facilities during
low flow in summer. Exceedances of the criteria for dieldrin were frequently observed during
high flow in fall. In contrast, no discernable seasonal pattern of criteria exceedance was
observed for PCBs. These findings suggested the potential impacts associated with seasonal
changes of bioavailable organochiorine distributions in surface waters and the significances
of considering seasonal, chemical-, and site-specific conditions in risk assessment and water
quality management.
114
Importantly, predicting bioconcentration from measured water concentrations of
bioavailable organic contaminants using passive sampling devices can provide more accurate
bioconcentration factor (BCF) compared to using conventional filtered water methodology.
Measured or predicted BCFs are an essential component of both human and environmental
risk assessment because BCFs illustrate the importance linkage between the water column
and its influence on exposure of aquatic organisms. BCFs are strongly influence prediction of
toxic effects, especially when chemical residue-based dose-response relationships are used
(Barron, 1990 and Cook and Burkhard, 1996). Many hydrophobic organic contaminants such
as PCBs and organochiorine pesticides have a high affinity for particulates and dissolved
organic matter, which can reduce bioavailability of chemicals, Predicting BCFs from
dissolved water concentrations using conventional filtered water methodology would include
contaminants associated with dissolved organic matter, which could not transport across
biomembranes. Thus, it will underestimate the BCF. In contrast, predicting BCFs using
passive sampling devices (BCFPSD) accounts for the bioavailability consideration and
consequently reduce uncertainty for site-specific bioavailability conditions.
The present study assesses the sampling device attributes. For instance, the passive
sampling technique can be successfully used to assess spatial and seasonal distribution of
bioavailable organochiorines in surface water, as well as, to allow a direct assessment of the
water quality based on bioavailable concentrations, as presented in Chapter 2. Also, it can be
used as a tool to assess the potential for direct exposure to hydrophobic organic contaminants
and to determine whether these contaminants are likely cause(s) of the adverse effect(s)
observed in aquatic organisms, as presented in Chapter 4 and Appendix E. However, an
inexpensive and simpler time-integrative passive sampling device is still needed.
In response to a growing need of an alternative passive sampling device, our research
group has further developed a triolein-free low density polyethylene membrane lay flat
tubing (LFT). Our laboratory and field verification demonstrated that the LFT without
triolein proved reliable and had the same benefits as SPMD, but was simpler, inexpensive
and lacked the interference from triolein impurities as found in SPMD. Our results found that
LFT tended to accumulate compounds with high log K0 faster than SPMD. Also, buildup of
biofouling on the device exterior surface and approaching equilibrium during field exposure
115
appeared not to be a concern as compared to SPMD. LFT sampling rates were estimated and
modeled for 33 target analytes, including PAHs, PCBs, and organochiorine pesticides. The
successful determination of field derived data illustrated the effectiveness and reliability of
LFT for environmental monitoring. Its application increases the range of tools available to
those involved in monitoring water quality. The method of choice for environmental
monitoring will depend on the contaminant nature and environmentally relevant
concentrations of contaminants as well as the objective of a study.
116
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Appendix A. Estimated river concentrations of bioavailable p, p' -DDT and its metabolites,
dieldrin, and PCBs (sum of 25 congeners) at the Willamette River during summer and fall
of 2001 to 2004. River concentrations were estimated from SPMD concentrations.
Deployments of SPMDs were typically 7- to 21-day long.
127
p,p'-DDE
p,p'-DDD
p,p'-DDT
(pg/L)
(pg/L)
(pgIL)
2-15
3-7
3-7
66 (5.3)
44
167 (49)
2.3 (3.3)
236 (51)
126
174
55
NA
250
514
NA
4
5
RM8
48
112
RM 12
15
18
11
13
59
56
20
46
11(4.1)
120 (1.5)
66
68
sampling event
detection limit
(pg/L) a
August 2001
RM 1
RM3.5 West
RM 3.5 East
RM7 West
RM 7 East
RM13
RM 15
RM 17
RM 18c
September 2001
RIvI 1
RM 3.5 West
RM 3.5 East
RM7 West
kM 7 East
125
48
NA
bdl
bdl
DDTs
(pg!L)
309
687
NA
161
dieldrin
(pgIL)
PCBs
(pg/L)
3-19
06954b
43 (2.0)
47
58
57
NA
75
42
13 (11)
14
31
31
NA
13
14
18
5
74
79
bdl
31
72
23
37
4.8
13
42(25)
7.5 (11)
60(40)
35 (15)
10(8.2)
289 (32)
327
6.0 (8.5)
bdl
bdl
414 (39)
393
439
65 (2.5)
50
120 (13)
94
100
NA
1257
55
108
NA
595
NA
NA
71
123
12
13
11
134
115
184
41
8.5
89
201
371
956
NA
NA
114
bdl
bdl
33
481
112
73
144
61
18
111
34
50
38
63
RM 18c
October 2001
21(0.77)
57 (68)
4.6 (6.5)
82 (60)
45 (3.0)
13 (4.8)
RIvI 1
82 (10)
NA
NA
125 (18)
NA
NA
266
NA
35
25
34
32 (3.7)
NA
NA
239 (25)
NA
NA
56 (2.7)
NA
NA
59
NA
34
40
40
130 (0.35)
NA
NA
72
NA
36
29
26
13
20
28 (2.8)
RM8
RM12
RM13
RM15
RM17
kM 3.5 West
RM 3.5 East
22
28
30
RM7West
87
RM 7 East
NA
RM8
RM12
33
RM 13
27
23
RM15
RM17
RIvI 18c
November 2001
RM 1
21
18
26(0.32)
71
73
kM 3.5 West
NA
NA
RM3.5East
RM7 West
114
93
RM 7 East
NA
50
46
140
180
NA
RM8
RM 12
RM 13
RM 15
RM 17
RM 18
July 2002
RM 1
R1v13.5 West
33
14
4.2
17
168
521
NA
NA
14
83
18
10
64
79
45
31
16
13
51
26
21
16(0.12)
69 (2.4)
62(0.44)
35 (1.1)
170
75
NA
18
26
NA
76
76
NA
22
32
26
NA
27
42
29
30
NA
44(11)
95 (6.3)
7.1 (0.72)
54
159
13
67
56
50
63
21
18
NA
NA
330
349
NA
104
105
135
106
98
NA
146 (18)
226
104
NA
NA
270
94
NA
78
101
83
102
104
49
100
37
105
NA
NA
24(1.2)
11(1.7)
54
33
137
81
101
128
sampling event
detection limit
(pg/L) a
p,p'-DDE
p,p'-DDD
p,p'-DDT
(pgIL)
(pg/L)
(pg/L)
2-15
3-7
3-7
147
14
143
212
1242
53
NA
NA
13
126
76
NA
65
RM3.5East
RM7 West
52
160
RM 7 East
NA
RM8
RM12
RM13
43
25
45
24
29
RM 15
RM 17
RM 18c
August 2002
RIvI 1
RM3.SWest
RM3.5East
RM7 West
RM7 East
RM8
RM12
RM 13
RM 15
RM17
RM 18c
September 2002
RM 1
RM 3.5 West
RM3.SEast
RM 7 West
RM 7 East d
RM8
RM12
RM13
RM15
RM17
RM18C
November 2002
RM 1
939
NA
70
42
9
DDTs
(pg/L)
dieldrin
(pgIL)
PCBs
(pg/L)
3-19
06954b
71
52
47
NA
35
51
13
74
38
50
44 (15)
32
6.4
8.5
68
8
30
31
8
7
121
63
68
18 (4.1)
24 (6.5)
4.3 (1.3)
47 (12)
52 (2.5)c
17 (1.8)c
154 (34)C
300
319
1465
28 (0.97)c
62
66
129
85 (2.6)c
218
229
1207
NA
NA
NA
NA
37
23
25
23
23
18 (4.1)
63
33
12
112
10
41
33
31
11
66
76
48
41
47
13
65
67
46
60
25 (5.3)
10(2.4)
53 (12)
41(7.3)
12 (2.6)
49(2.5)
96(18)
NA
175
18
759
68 (21)
74
20 (12)
156 (22)
NA
245
923
126 (39)
74
26(2.2)
NA
11(1.8)
NA
32(5.6)
NA
52
90
37 (10)
27
22
29
NA
56
52
55 (42)
24
61
66
20
24
130
NA
9
67
8.1 (2.7)
15
45
60
52
NA
37
19
26
9.3
11
11
58
78
43
39
27 (10)
28
28
30
7
49
23
8
39
22
3.0
bdl
22(1.3)
9.8(1.1)
50(1.7)
33(0.14)
9.5(1.6)
204 (16)
200
83 (8.0)
29(3.5)
69
65
32
37
30
16 (3.7)
39
7
11
21
25
38
22
15
16
18(0.61)
91(3.6)
102(11)
11(1.2)
RM3.5 West
78
108
RM 3.5 East
79
RM7 West
61
129
14
14
321
RM 7 East C
43 (4.8)
41(5.4)
37
38
RM 15
45
47
RM17
153
55
7.6 (0.079)
505
92 (10)
28
24
7
9
13
35
27
7
9
6
73
70
88
83
27
13
5.6
29
4.9
bdl
52(8.0)
37(9.2)
10(1.1)
99(18)
84(24)
51(7.3)
76 (12)
14 (1.5)
36
37
260 (18)
332
47 (2.6)
54
RM3.SEast
RM7West
170 (4.5)
242
242
426
48 (2.6)
54
59
105
338
61
149
61
47 (8.9)
51(12)
8.9 (6.9)
680
107 (25)
48
RM 7 East e
40 (22)
41(14)
RM8
RM12
RM13
RM18C
October 2003
RM 1'
RM 3.5 West
8
64
50 (0.29)
46
46
53
53
12
22
10
69
102
129
sampling event
detection limit
(pg/L) a
RM8
RM12
RM13
RM 15.5
RM 17
RIvI 18.5
November 2003
RM 1
RM 3.5 West
RM 3.5 East
RM7 West
RM 7 East
C
RM8
RM 12
RM13
RM15
RM 17
RM18
July 2004
RM ic
p,p'-DDE
p,p'-DDD
p,p'-DDT
(pgIL)
(pgIL)
(pg/L)
2-15
3-7
3-7
24
NA
NA
23
34
6
65
NA
NA
26
NA
NA
49
30
29
14 (0.53)
527 (35)
NA
322
533
131 (13)
13
16
127
101
20
139
118
93
91
68
17
16
16
35 (2.7)
55
47
52
39
45
50
13
14
17
15
NA
NA
bdl
bdl
bdl
264 (17)
NA
223 (8.1)
NA
39 (9.6)
NA
119
37
102
166
199
67 (6.7)
70
58
81
69
53
54
232
50 (6.0)
44
26
38
32
24
21
DDTs
(pg/L)
102 (7.4)
234
9.0 (0.18)
161 (9.5)
21
RM3.5East
50 (1.9)
57
42
133
RM7 West
111
RM7East
RM8
29
804
66
54
14
132
8
8
RM 12
28
RM13
RM15
RM17
28
23
RM3.5 West
RM 18c
August 2004
RM 1
RM 3.5 West
RM3.5East
RM7 West
RM 7 East
RM8
RM12
RM13
dieldrin
PCBs
(pgIL)
(pg!L)
3-19
0.69- 54b
34
NA
NA
NA
NA
35
24
29
bdl
bdl
76 (5.9)
NA
86
76
67 (2.8)
64
60
74
58
62
35
1.5
39 (3.5)
NA
80
22
15 (6.7)
13
bdl
5.4
4.3
bdl
5.5
90 (6.3)
39
39
bdl
34
28
43
6
9
311
188
1046
103
88
67
75
58
86
19 (4.4)
22(2.9)
6.0 (1.3)
47 (8.5)
38 (7.6)
42 (3.3)
91(0.52)
126 (2.1)
56 (1.1)
95 (2.9)
149
120
25
273 (2.7)
236
68 (2.8)
63
52
106
NA
30
25
62
65
69
152
123
116
NA
67
68
60
68
NA
26
546
NA
50
7
29
161
201
813
NA
NA
11
13
91
45
43
64
128
154
126
99
90
89
90
42
34
RM17
31
19
20
8
74
83
90
48
51
104
69
92
51
35
RM 18C
23 (0.23)
29(1.0)
15 (5.2)
67(4.0)
60(2.0)
53 (4.6)
122 (1.1)
70
139 (3.0)
108 (1.5)
260 (3.1)
RM 3.5 East
82
28 (0.27)
29
29
290 (4.4)
RM3.5 West
RM7 West
282
71
93
105
RM7East
RM8
31
152
408
184
63
95
64
RM 15
October 2004
RM 1
RM12
RM13
28
45
32
56
36
37
43
104
98
18
17
656
30
403
41
10
10
203
209
1341
69
96
71
21
129
28
53
8
66
85
69
84
162
130
sampling event
detection limit
(pg/L) a
RM15
RM17
p,p'-DDE
p,p'-DDD
p,p'-DDT
(pg/L)
(pg/L)
(pg/L)
2-15
3-7
3-7
49
39
10
37
27
47 (0.93)
9
18 (1.2)
DDTs
(pg/L)
dieldrin
(pg/L)
(pg/L)
3-19
0.69-54'
PCBs
46
49
RM 18c
58 (0.58)
124 (2.7)
68 (3.2)
n = 1 composite sample of 5 SPMDs; duplicate samples were at River Mile 1 and 18; values in parenthesis
are 1SD; bdl- below detection limit; NA-data not available
a
range of method detection limits from 13 sampling events
b
detection limits for 25 individual PCB congeners
Cn
d
2
19
15
98
73
86
86
123 (0.90)
131
Appendix B. Sewer overflow points in Portland area (City of Portland, 2004,
http://www.portlandonli ne.corn/bes/index.cfm9c=29323)
area of former POB using
facilities
RM
COLUMBIA RIVER
sewer overflow points
RM
sewer overflow points
(99% eliminated on the Slough)
/
RM7
sampling sites
COLUMBIA SLOUGH
RM\
WILLAMETTE RIVER
4
RM13
RM 17
RM isL\
COMWNED
SEWER
AREA
132
Appendix C. Equations used to estimate molecular diffusitivity in water (D1
kT
=
Stokes-Einstein relation
67trr1
)
where
k = the Boltzmann constant
(1.381 x 1023 kg m2 s2 K1)
= dynamic viscosity (kg rn1
T = temperature (K)
r, = molecular radius
= [3Vj/41tNA]L3
where
V = molar volume of the chemical
(cm3 moi')
NA = Avogadro's number
(6.02 x 1023 mol')
=
Hayduk and Laudie
13.26 x 10
1.14
v
where
= solution viscosity (102 g cm1 s')
at the temperature of interest
V = molar volume of the chemical
(cm3 mol')
133
Appendix D. Predicted values for LFT sampling rates using different methods.
3.4
.
3.2
C,
ci)
C)
predicted R from water
diffusion coefficient by
Strokes- Einstein at 9 °C
-c
:3
3.0
predicted R from water
diffusion coefficient by
Hayduk & Laudie at 9 °C
.
4.8
4.4
4.0
S
2.8
ci)
0
ci)
c.
5.2
S
3.6
ci)
2.6
S
..
3.2
2.4
2.8
100
150
200
250
300
350
100
150
molar volume (cm3/mol)
5.0
4.8
4.4 (:1
ci)
Strokes-Einstein at 22 °C
S
7.5
I
C))
S
-c
S
4.2 -
ci)
0
-c
4.0
ci)
S
S
3.8 -
.
ci
S
3.6
100
150
200
250
300
.
300
350
7.0
predicted R from water
diffusion oefficient by
6.5
Hayduk&Laudieat22°C
6.0
S
5.5 5.0
4.5 4.0
350
100
200
150
molar volume (cm3/mol)
250
300
350
molar volume (cm3!mol)
25
12
estimated RSLFT from R$sPMD
10.
-j
250
200
molar volume (cm3/mol)
predicted R from water
diffusion coefficient by
S
4.6 -
ci)
S.
S
estimated RSLFT from RSsPMD
-c
:3
S
8-
U-
I
S
ci)
20-
S
$
15S
.
2-
.
S
.
10S
cci
E
.
S
S
5-
..
ci)
S
0
0
100
150
200
250
300
molar volume (cm3/mol)
350
100
150
200
250
300
molar volume (cm3/mol)
350
134
Appendix E. "Environmental stresses and skeletal deformities infishfrom the Willamette
River, Oregon ".
Reproduced with permission from
Environmental Science and Technology 2005, 39( 10), 3495-3506.
Copyright 2005 American chemistry Society.
135
'1
&'.
"''". 2005, 39. 345m5"3S06
Environmental Stjesses and Skeletal
Deformities in Fish from the
Willamette River. Oregon
eitiI of evidence suggests that
parasitic infection, not chemical contaminants, was
the primary cause of skeletal deformities observed in
River snails. Thus, the'
SVillamotte River fish.
DANIEl, L. VILLENFUVE..
Intrnductioo
MICHAEL Ii. CtJNNtNGfl&M
DOUGLAS F .MARKLE,
'the Wihlanit'tte ttae'ruo we.b.': Lit rep. it I iiii' 'itt I American
thu 1t14r tlivcrs md e'ejvs's nl.jrc rail It ir square tulle
w:iteixliii] ituami ;mtiv',Iijo'r nyu ui ih.,' tJ.S
hi llcmwsnurih
for tft nuilcs Itnutigh 'fluxed .ugii.,'iiltiir:ul ::iisi urban areas
tuItnItill,'I, (i1'.'g..iL'Ctal'19.'sl un5'lrCpohio'anarea,bcIori'oining
LAWRENCE Ii Ctt tills,
JEFFREY I Jtt FINS,' KARA F. WARNI It,
FRED T1LTO1'1, MICIJ.'%t I. L. KENT.!
VI ItGI N IA C. tEAT RA F.
.
000LALAI SET F1AJINTAN1N,
ORAPUIN XRISSANAKRIANGKRAI.
thc o:.Ji ulia l0;'s'r tigoiri' I'. 'I'hc\S'IIlainetIe haslitishionni
to 10'.. ti 1r1'g.iliians. aid hio'ttltlaiiieno' tatlo'.' Isi neil the
ROBERT GROVE, AND
mot hiht' pititirtivo' .igrkuttuiat ro'gli.ns In the' PacIfic
Ni uhner',t ' ' i
is a significant
'tic \Vlttaiuc
EUGENE R.JOHNSON,'
KIM A , .'tNDERSO2.
I )',rin:o'nt ol F :r,:/,:fl.,,/ a.'ui iF'/,r'I(
IA' iflus it of Mrr4wOxr. oi:,I I),'pr .0:: :i J
I i'iIdI.J. Oovgon
'a.'.'
.':.'r..ai
0. or: a 9,'
,
:a a
ingrait'xriidon,nurserr. ttndsp:IwnhuuglutohiLmi lorsalinii,
and ne:J'l\'.pi slociLet ottisli xc horn id5'niulirdixo lbs river
3,. tli'i'FC:lili'ilLll Itching is i1lllxr, aid reciiho'uut speLls's are
fistird OhiO 'tll)l 'it I tic'. s'ai
too thu cturh' 110 is. the .ure'g.':tu 15.1'.. tinciot of En'dromo.
mti nec siiptiiio os if sk'tc tat di'forinitk's
nh'nt'al ç'u,ih:tv r011
The Willanierte River, one of 14 American Heritape Ricts,
fhOiA:S tliioughi the most densely populated and ajri:.ultnrxll'
productive reon cf Oropon. Previous hioloqical nloIotorxxJ
of the WI axiette River detected ci toted frequencies of
sitoletal d omCtios in fish from certain areas of the lower
oJIewberg pool INPL rixerwile IRMI 2E-55 and middle
oWhoatland Ferr fVFJ, FM 72-74i rover, relative to those
in the upper river iCnr.'allis CV1 RM 125-135). The
objective of this study was to determine the likely cause
of these skeletal cleforntities. In 2092 and 2003. deformity
loads in Willaisotte Ro;or fishes were 2-3 times :preater
at the NP and WF lo':ati:.ns than at the CV location. There
wore some differences in water quality parameters
between the NP and CV sites but they did tot readily'
explain the difference in deformity loads. Concentrations
ofhioavailablu metals were be!:.. ci election limits 10.0-1 ag;'
Lf. Concentrations of hioavailahle pot, blorinateci
biphenyls )PCBsi and chlorinatnd pesticides worn goiiorzi!k
below 0.25 ng/L Concentriotiw of hi':'.i':nilable lsaiv:x:.lic
aromatic hydrocarbons were generally less than 5 n;jL.
Concentrations of most persistent organic poilataits core
below detectron lies its in na r.c: : do tiosue s..amp ls
and sediments, arid thcso that 5sero ctiecteci were not
significantly different amonrj sites. Bic'.;say cf Willanoette
Rwerwater estrants l:r':'.'i':leci no eviclencethzt unidentified
compounds or the ortople.n nioture of compounds present
in the o'.'trx
ould icluc e skeletal cloforniities in
cyprinid tisli. Howo':or. eeiaorcarise of a digenean
treisatoclew ore directly aw.t toted 'fth a large por:'entage
of deformities detected in tcn Vcilltnette P i or fishes,.
and similar detoruitties '. re reproduc ccl in I;!'.. 'ratory fathead
minnovs exposed to cercaris
oyrrri;tx1 from Willantette
In tvillaiuieiti' Ricer i'isl's. hii.togical nliillitiring has been
vyi,t'xlx' used I.' o'y,ilu;uc .lquatic es:t's''ste'nl health and
lli'1iit.i iinpacs 'it anthorupegemiii' aclivilirs 04 has been
sil4ge5k'Ll hal skeletal di'tonnhiirs in fish sCulL .15 a usefut
hiiiindii',uii' uf Ijiltiti"..........;, and c'iiluiiiiin sk'ls'ltil
:l;'firniie',. in iu'i'n0hi' itt has Ito used lit itiotilijif liii'
1
licti populaunos iiIn I 0192-103.1, thstnckhencs'
I lske'tt'Lit itoh ritiiii' inntil unit pikemlIin000' iIri'iiri,''iu'ii,io
hc,ihthi
a0'301't?o,'5l i'iihlc'ctcct from
tlii' \cwlii'rg
, P1 rcgi:'ul , cx-
io'nding horn liver mite htMl 55 to 20.5 Figitri' I, r,nigi'd
1'. i 14'- 13, Nmnth ..ii pike'iniuin in' ske'leiul
'''un 24 i
4xt',urttiIv rift. scc're tilso, cli'raied rl5"i(,, in this' ntdctk
tVihl,uiiucilr urn ,i.und tiM 12 \Vhi'atlont him'; Figimic ii,
Its C',litF,ist, the skch'L,d shcl&rniiit' Cxii's Ut juvenile noruhit'nn
plLs'ntiIonn'c' e' .5 'ctd from the' otpper \\:1tlann.lt Ei','c'r tiM
25 r.uy'd loin iii to 51''.', '12-- !Si. Northern
piio'mmiiitiiuw ails U' t the timil' sporE's unpacte'it. tiltS species
cahlccued Iron liii' Nw'lmc'rg region and associ;mrcd ttibutaries
in 4's'. sku'Icitil deli 0 0111'. rats's t'tt'5','ot'd2s''t in tn species
4/J As ii to'1 'Ii', t,i'muo',nit,,ri ig .1 skututal ds'tc'mxocies in
tVibt:mwo'LL
river hisli supposEd that fish 'ruin Otis' Newherg
re5 'mu ;uod ttiiddhe tVihlaiiio'tie l(t'rr hash signiil canthv greater
di on oily rates thor Itoh from the upper Vtttajnc'tt
Direr.
In the nil-tic t i05 Pi'hbtS;ih5 ii tsp the Nes'tbm'rg 'eon
of lie' V'iltayi,'ti5' liver as a source
ihi'lr king wato:u hit
uthan cxpuulsion hieiuhtcuoi'd poibhic cxnc'L'rn rehiic'ib to the'
rc'prLs at uti'l mud fish Ii ttp: ,'.;',cicw. IniViuiiCt.i...1110/ safeV.'illcl' ii ,'vs'nlnl:'v'r011mmnme tuir, ' In 1040, liii s"eainphc'. 115% of
11e'OPli' siirvo'vc'd ua.prcoiss'd 'e'xln'unc " c" icons abut the hcvc'l
1)1 tuidld' chui-inicxis in the liver mu.l's'gJu Daily JIino'r2ld lob.
20. tsiolOt, 'ill it research tsas a rcsponse to such CotiCCifls
and, especially. scienithc ox i. 'nolan' concerning potential
causes,
il
A with' tarOt 1':
ct':muthcih, pho'si rat, and biologurat
stressnurs I:,uec Noon fls:,ji'tdLi'd wi Ito ski'ht'tul ilrftrrniths'c In
fish. A v,,l'i'l'.' 'b' ctjemiurtilt, miduiding tue'a'w' iiinats, sue'ti as
k'ld 'iii ulttulur'itiiis iutiY:'plulcpttluli' pcsliridcs, ao' kaii.no'n
Corrxipooiiiauthsorptuiia': 541 .7,7.5yiIfl;5.jr 1511i7:07i In?;
o-rnaiL ksoo.and'rso
got iats'.t'iii.
to induce ne'tlu','ilimusi'uI,' tanitugi' thou can result itt sk'o'tm'ial
0). Chs'nuicals can tulsa cause ski' trial
del Uffl0i lid's
Curreioi address: US EPA Mid.i:'.muieoit Ecology LaIis.:.
Duluth, Mituiesoto.
flioparirneni ot Mir.robiolcigv,
Otlupanment oil FL u'ries trot Wildlife.
drive iuuius'shv tin iui lung mItsuI .11liio'iitilh lit 101555cc wish bane
Dopariruent or Envirriioiioonlal tad Malaulir liixiroio4v.
lO.lO2iioO4R57O ccc $3725
Publishsd Sri Wsb OOlOtZCOS
2005
cis,,,xe 5,,istv
fornatiu 'mu, 'imp nods such as 21t,7.ti-ti'trtuchilornutfisenzo.
p.dioxin, p.1 vi'hho,rinuir'd hiplio'nvbo.. toaaphene, and castmiuin bays' b.oe'o'mu reported to sOuse keIntab deiormIl'ks
S'OL. 24. NO, 10, 2005 !ENViRQOJMENTALOaENCE & TECHNOLOI3V 3&9
136
N
najorthbutary.ntr
D Primary study Sites
City locations for
geographic reference
I Dirctlonofflow
FIGURE 1.
Diagram of rite Willatnette Basis depictinoj the general location anti course cml the Wi)lamemie River and pminuary study locations.
thmugh such mechanisms / 0-21). Skeletal rictormitmis have
also been linked to water quality problems. iiwltmding ow
p1t (25-26) low dissolved oxygen 27-2W. and elevated
tentperatures t29-301. Nutntiutsal deficits. panic uiarlv ascor-
bic actd amid trvptophan deficiencies, have been linked to
skeletal deformitIes in fish (31-32). Inbreeding hasalso hecum
shown to cause skeletal deformities, Including scotiosk.
lordosis, cut-ved neural spines. timsed vertebrae. and coinpressed vertebrae (33-35). Finally. ttmmmerous infectious
biological agents, including viruses, bacteria, and par ashes,
have beets reported to cause keietal de[urunitics 36-39).
Although the association of fish skeletal deformities with a
sslde variety of stressors makes it a useful endpoint (or
biological monitoring, the observation ni a high incidence
of skeletal deformities, alone, has little diagnostic value.
The purpose of this study was to identify or d)agtsoc the
causels) of skeletal deforrnitis's associated with 'yVIll;mnie))e
Riverfish, with particular ewphasis rn the Newberg region.
Skeletal deforniiries in fish collected front the upper. middle,
and lower Willanunc River to 2002 and 2003 were cliaracterizedtodetctrnincwhetherreceun prcvalrnccswerestniiimr
to thm.se reported previously and to further describe spatIal
arid tetnporal patterns. In situ monitoring of river water
quality coupled with in situ santpling amid amsatesis of
bivavailahle organic cuntantinants mid metal', was used it>
compare water quality and potential for direct exposure to
knowia chemical contaminants at the Newberg amid Corvallis
study sites and determine whether these factors were likely
causes of the deformities. Analysis and comparison ol
sedlmentsamplesand fish ttsucfrom Newbcrgmwd t.orvaflls
was used to evaluate potential iropltic or maternal transfer
cii known
organic pollutants IPOPsI usa powniirui
cause. Bioassay of river water extracts using embryolarval
fathead nsinmiows (Pimepitcth'.c prome1al exposed under
controlled laboratory conditions was used to evaluate the
potential role of ttriknown chemicals or complex chemical
mixtures In causing rite skeletal deksrrnities observed iii
Willamette River fish. Field-collected fish were exatstincd for
parasites, and the association of parasitic infection e.lih
skeletal defonnittes was quantified. Finally, cercartae of a
trc'tnatode parasite Identified as Apopira/Ius dopt lens) were
collected from Wihl.atnrtte River snails (1-iwoin len/a s.rr'#m,s,
(lie interttsediaie host for A c/on/cm). and fathead ntinnr,ws
3496 ENV)uONSIENTAL aCIENCE & TECHNOLOGY VOL. 35. NO. 10, 200t
v/Crc exposed to the cercarise in the laboratory, together.
these components prosided a wcigtmi-of-evidetsce-based,
empirical approach to identify the likely cause of skeletal
sicfonuu ties in \ViIiucmtettc Riser fishes.
fsletliods
lJsJ CoIIes'tiu mum stint I )e'kmruiiitv ( liaracle',iirullimn. larval and
juvenile tlsh y;rre sampled Irons May to October 2002 and
Mayto August 2(511. lists were collected hr beach seine, cast
net, and dip net. The three primary sampling areas were
Ncwberg pool (NP: JiM ITSSI: lower Willanteitmo, Wheatand Ferry livE; liNt 72 71: middle Wiilrsmeue). andCorvahlis
hiM l25-13t3 tipper Mllamnetteu. specittaerms were euthanized with an overdose of MS-222 ltinquel itricairse nwth.mnesulionatei Argent Chemical laboratories, Redmond. WA
:11 500 Pl>00 and tixed In 10% bUft5'rt'd fornsaitn Seventeen
species were collected, with Puvm'/mocl wi/u.s ois'goncnvls Inoribertu pikensiniouw). Rwimaniaomus baiter/us lredtide shiner.
mflo.stonncs nmuermc'/ttnilu.s tlargescale socket), Mi'/rs'/o'i/us
eanrinus I lem tithi . ci tad .'tcrom'hetht.c a/muuncetas (chisel-
moutlu representing the most commonly collected species
total sample sizes 1000) 1/Ui.
Spectmcns fixed icir a mInimum of two week>> wereX-raved
in a Faxitron MX-2i1 cabinet X-ray machine lining AGFA
SiructtirLx li-I t)VET1i Industrial rsdiograph film. IL in was
developed ustog a Kodak X-OMAT model MOB developer.
1 5 700 usIa were inspected (or deformities
using a 10 lOx ocular over a light table. Presence or absence
of 12 different categories of skeletal deformities was scored
additional tietailsimi ref/U). and our analyses were based on
the number of deformity categories presemit per individual
Radiograph>> of
deformitY load,i 11 /u pius the number of precatidal deformities. since casmdal deformities mitt' unufuurmis disoribtited ) 10).
On the basis of randomree'.'aluatlon o(550 (ISIS, readercrror
was not significant Ub.
In Situ Waler Quality aim ii Jilt avaIlable ntrmuhmauuts.
SEW iJs'seriptiout viii! Saunpin' (o/iertioum, Willmsnst'tte River
sampling sites wect' chosen to facilitate tm'estigatlon of
sc'asrtnah mind spatial bioavailable contaminant concentrations
cit Newberg and Corvallis (Ptgure I). Two sampling stations
were located at Newberg, tune itt the south side of the river
tiM IT; N 451602' W 12254.OiN) rind (mite a fw miles
137
dtii wrot the nt Is side of the rivet filM 44: N IS 1527
W 122 532iiJ. 1 so
liii us wow located SLt (ti rvallis filM
i35 Ii N 45 20.15, V 122 .51.00: j2j N .I52..sT. W
1223iL47'i .NLwbun stauuit I tiM IS sees about 25-SO ft
froni the soicUise. and 11w l.j-al teaser depth was 27 15.
Ii fro' ii die shore,
and the irte iwater depth was 20 It. 11th (.orti1Ii statirros
were about 15 ft from the share, and tlw I eel water depth
Newlaerg statIon 2 IbM 11) was about
quantilt: afi n of urganochrloeltics, ongarionll'rogen lristtcidus,
:itiI . t'Oitti Iris plt.ltr' ps'stic ties ate' pr 'sided elscs. hit s' till Thu t'lvcrdilc ari'tu;tl Ic hvdros-arho its Pt! I" ontatnimills freeti'ln let'. 'elitnilicle ciIcenuaIcl to - (liii.. 'fill
ditt'ctt 'Ii tush qlertuttiari Ii 55,15 pi'rliriiiu'd lilt ii F [PLC: tutu
dual di-lecttcar ho lilt:: vs eon' cit Iiride tire'-, hth with
I
ttaitlliple wat'u'l'rlgtllr. Site lit' recencr' detector had an
cxciht:ott w.u'oli'mmgth at 2211 tril cnticsion ss'avelettgihs at
till, arid Ito am: il,' lied' ccliv lt:mtI sktcctioim signals
tv and 2%) not. I ttts' ti:r'e',' clintpl.utsds Ilnorene,
was 7-U ft. Flow near the Cea-s'allt.s stics iii Slav 2tr112 wits
-P0Ot) to I 0 000 ui1s andhv late Jute lied deretsdti
ft3fs. AL the Newberg cites, flow In S1a 2r't'j2 ss as 17 (Jr.JO itt
'lILt
20ii00 11'!s oral by la:; July i-icasid ii 7111' il/s, lire
Coivallisarsta was gencreiiv hllts........12 Itj intl characterized by shallow gravol and srdlntcni riptuip. iti the Ncwherg
area, the Willaurutic liver was at tich ii ecp;'r ;0--Or itt, and
there were no shallow gravel reds ncr In' s; 'ide sites. The
Willarnette River hiss vet-c .roep hairks at ftc cwlrerg area:
withIn 5-10 ft of the bank the Liver lt I 5lit ft deep. 'the
bottotasof the nyu iii iiiisw' ii IS a urubittati.ii f o:L jial
mud.
Water satnp1urg was curtdri neil ii oat ho to loS; in
and 2003. Thi'u; 2 1-rI satttplittg tV'tltS wre curcrpkhrd per
hr di lii' array: the rest were yf,;, r-cte'iI with lit' tluorecetrcc
detector. Thu' colunin set) we'. .1 'lieit.'liluctiex Luna Pitt,
with '5-tins particle sIze. The itt-il U tnt-ut 5çJ5 run sf111 a
constant 11w utile ofti.75 ttttinuitt atil a united gradiens for
year, one oacliin app: airnatel:- 5.1:10. 1 ;uiv. and liLly. Sampling
evelits were designed to diaracierizr' river conditions during
spawning and early developin em. N ulrieu I and waler quality
parameters. including dissolved iisvgrn. spvthc conductance, salinity, tots dlssrrl',ed i lids. lctltper:Ltii Lit, J)iI, OPt'
foxidatlon reriurti on poten ii al ileptli, a ilunonlum, IlitI its',
and turbidity, 0. c-re collected art OIL hourly basis tslth a iSt
13i120 Sonde ifi. i'ellmc Springy. OW
Dissolved, btoavailahlc' llrgani ; 1 nfant:ieauts and metals
were cotlected 1w dcplovii'tg patsisti si n:liiiig i criers rPM ii
and diffusive gradient tltinftliits it)(,t'r in pIJtcL'tivr' irish
cages. PSOs COL1MOS d ti neutial lipid Ii -. . tn. dclii enclosed
in larilat polymers; :ibing lnvironmuistal Setup lug Techatologlos. SI. I wPii, ML)i I/i live itidisldita] PS1)s and ne
n;'r pxsr liese inch Ltd. 11151 ieee mcmii ed ill each cage.
Each cage was tisprided with a 'il'.at-;.ii'L-cage-c.ii'lcanchor' arrangatnetit that nsuicd that thy uagew nidsiar
at the station and toO ti slav suspen dud tie iLl loin the
liverbottomThellvc ISISs isL'LS' IcOn rrrnrpostted tin analysis
PSOs and i)G'Fs were kept on mee iii scaled, airtight, atitbet
glass cuttlalners dtiring ttattsport to and I torn the field sites.
complete I'S!) descriptions have been published 1121 P51)5
weos' gent lv cleaned ci: sediunent or algae abut deployment
at the site utilizing .t tub tilled with site water to minimize
air exposure. \'i fouling impedance was entphsr ed its
eaJunitjtiojis 1 estimated water c'tict'riiratioti, since algae
grossih on the deitce-s was till to tnmninial.
inifrt:cru it'oo ,t:oe'. PM,ts wci'i' exit acted by hesitito
dialyses. inainber glass iUs, Sample vrslorries vote reduced
using aTutboviap LV /ZvnIatk Corp tlopietiten. Mi. The
samples were then run through gel pemlesition cltr,,rjtlatlgraph IGPC) lenodels SIS pump. 2487 dual ictveiengtli
absorbance detection, 71.7 auto-sampler, and inricun rollectorli, Waters. Corp Millard Mi, at id fiactlotiscoir raining
ergannchtonintr pesticides. sagan pit osph. ii' pestiekl'-.. 'Snganonitrogenpeoticidru. rt:Iis,atill'Siris v.10 cilk'c-tcd.'lhe
Sat. tutu dls4ttvlhrcttzenc
GPC calun'inc 5.-ore
not
eopolvmerparticles. 1 5-urn particle size awl I IiIS_\ Itiresize.
The GPC progratn ran with lull;, d ich I 'it iv Italic ai 5.0
1
LI
mlimin. Appnopriatelraeu ins were ds'tenttitied hv-ataatralng
standards and furtilied ststtspler t. ii. split lItre::; ractions
went analyzed using c;i:-dtr:rl-o:ti itl'gLiIrchl.rriite-1), 15(5dual-NIt) ol'ganttnito gull arid organ pltIspliale pesticides)
and HPLC- l)At) and Ilnoreseettee flit [sit li: ut.rso\, Agileni
Technologies. PalAlto i:5and ibIs' 11110. t"tewlett-Packard.
L,
I
PttlAltrs (Sir. Sanaple maniptilati. tiswei'e ps-rforiited in L'ttltet
brown amber or foil-strapped glass c''Itt:Liners to minimize
TJV(vis exposure. Detailed analytical tnethods used lot
i'. 25 I.
c enaplitltdene. anti iitdn it' 11: :',t p rca:. s-tire detected
the ttcet.luut rilu'J 'rUt er 'lutin t svslettt tIn: LOtte prognant ran
at ii':, aeclunitrile fin 10 tom, was gr:tdu:tllv ramped up to
70% cet'itiitrile fir 15 00 ri. arid tbsetr rattiped tip in 110%
tacct'trittitv for if inlet, 'liii' trISIttli sea'- held it ISiS
acetotuir: k or miii and then ret::: i'd In lt'iC- atid mimalveed
by 1111(5 with diode array detecli in INtl II itd 11 tumescence
dets em ion. The approximate reknit 'n 11101's ii ni lii are
naplsthiiune, I 6.0: acenaphtbtvk-txe. 16,5: 11w -reLic' 1$ P
ithenanhlirene. 18,15: anthracene, 18,6: ihtorattLhene, 19.0:
prIetic'. 211.1'): chriene, 2si 4: bs'nzull'd antltr:mcc-rtr'. 22.1;
heniotiIitfluoranthene. 24.5. besrzoikilluoriinlhene', 21 8: betshetvoit i
7010 [ISTCIIC 2r I dihuti/oli itletit4sr'5uet5u
pert-I tine, 2(1,8: road Indo I 1 .13.t-dipycene 29.2.
AflerD(il's wereretniu'ce'datcd in thu-lafrorotomy. thee resin-
gel was renies-ed -arid immersed fur 21 h to 1.)) ml. of I NI
truce metal guide tritric acid i.E"ir,lter scicittilici. Acetic acid
end sodium ,icettuti' went' used itS i}ri'srtpprttng electrolyte,
atid the- samples were diluted to all net volltine at 25 tal. sti Lh
III-?Itt ciii s-otter, the analysis seas 1st- atiodic stripping
cohtarnrtretrv Ast) i'l'raceiletect,Seattle. \VAi.Allgtebwater
sautup Ps ice e lii [ci ed rhrrt a 0 15-/ittt nw-tn ht'ane miller prior
luinct,ul am uslvscs by .V5'i', \SV wus used to tlrianuft ilte tstetis
iprurtel . Iiedttct I rn otet5tltils 5 ';t i' ''cr111 ccl whIt standards
each Itfetuil it'sly'd
r,:i.'fj:',"t' r 'litIOlt .',i,:. It'Ll, rti, .ini toni-lion blanks
lucre its..1111111 etch s.uaillitig cr1-Ill, Field hLlttd PSI)sant pIt's
'vane pencil oral esp setl 11 the stmnisplscru Itiriiig chc'p1-tatett I or ceo v'ry_ I teld blanks were ri ceased atid :inalvzed
eactiv as rlCJ'J L.;ed I'S!) samplers. Field ettr,teIt' 'us blanks
were ops-rted us lie held and wasltu'd sitttrtlallng th0 piocess
of ur't ii''ing thu light se".ilrnet tI or algae on the PilSStl e
sampling hcviccs. Satnples eultsitinuilg residues exceedIng
ihir' bLinks were coutsideccil pisiuis'e Ion residues, 1ltnsport
blank salutes 'sIn' ttiult plied Is the ss'ats'rvuikttnc than' would
have be'ui expIsorl to ii' cli with the uther VSI)s, The CorvallIs
sue was ds'sigiitsted as a lIvId dupli'arc' s102, Field duplicates
repuu'set:ted:':utU if :illsatnplescutllecli:d All l2('samnI'le type's
woe inchtideih in '.'.uebt ati,slvtic.th huatcht. 1.ahulurel, nv QC
'-..tttil'h's included rr'tgcttt blanks. loctilied saittples. and
al's-nature chli]rlieat's. Lacht (II' ti' t's'prcsentesl 5 10% uI
il,' intl nuiinbs'r il s.ursiples'ait,ilv.ed iii any given hotels.
thc'v were- prepareli ,tmtd ,'utalsved in the' sanie ldshion as the
field satmipl's. iii gaul c siatudat I '.i;lteutiSs-rsic-i'. West Chester.
tAt crtr'.'v-. 'isle tqliculll\.'oirlposed oh i: 1 standard conconirtit 'to .lttl.l tO i'ltil sttiiiLrrd I_Ole 505,0, Ward 11111. MiSI
cutest's ' ', lot tilt auual'.'scs.
581 Al/il,,.'' 'l'lte 11:' irs' and mathematical naodehs
requi rush Fir COttilistt is '1 .usalvte seater c'clncentratlons trim
the ci tte,'tmirdiioil iii In 1151) lIpid ltase bc'emt described /21.
The l,hlowliig 05Jul15 II lr':is tisel.i Lu rilculale the dissolved
bIoswatlahlet vttmti'i eousceilttaliOLu.
c
5, here c,., Is thu d'c ncenit'ation if ,inal1'e in seater,
Is
1/OL. 39, 11/0, 10, tOii,i ENvliRoclMENTALaclEraCs & TECiINCiLOG/. 3497
138
the concentratIon in lipid SP\ll)1 I is he exposure Unit in
da;.s Mspei is the 1n.ts A SPNJI) in g, and I ii tiic PSIJ
siunpilug rate. ainpliiig rates iI1j fur a large wncs of tIC
anti PAll contanhtttjnts [java beeti 1'rci u-h utaNe,hetl,
1he mass ni the rntt,il in tue liCt resin gel 11 was
detrtntnt'd mitt the .\.SV qwtntititt n. iii ic nv and
niathematical In idik required for Cii ilnatitli Lii jttaI
waLer t-uncentrati its from tile cuneentrati n ill the DCT
have been previously described i i i. 1 he fr lkwiug equation
was used to calculate the labile (bjoasaiiublet water con-
N 15 iS .100 \V 22 59 161) - and three samples were' coilected
0 21 .567. \V 127 15111. In 003.
Liii ic samples wi-ri- collecteil at Neschet g location N
'15 15 57, W 122 5 12
md three samples -tet-re colkicii-'d
atCnrvtiilis hicatein N 11 2 0017', tV 122 15-1.12, Sediitteni
samples welt cc jt'd ditectta into certiticil I-Client j:trs.
transported -ta :c.- the labo: ttsny. and ct-i ed itt - 212
at Coty,tllis Iticotion N
1
I
1
-
Until shipped lit-attalesis. m'dluttent santpleswere ixirucied
and timiaivi'd Itir 22 i-iilritt:itecl pesiit-iltt-s he ii 511:1 lA
milItiA 01i21.i, - ml rEt, igcn.'pltisphtrtms llLstlLuCli-S hr I 7-'
NEll, hod 3' 'Itt clttlgetti.-ts by I tittit lit-',-\ ittethod )tutl2
At ii) the ilIEQ l-tiboruti,ra, I'nrtland, tilt, Mills for chlot't-
crtttrat.ittn.
nated pesticides atid Pitt', u-crc -Ci.33 ,501'Kg wet sat. The
Mill, for nitrugen'phcphiiitts pe'stit-ides smas lOsig/Kg wit
where C. vet', the eoncentrtU a 1 iuettds in the 1 sl I tNt)
eltttionsoiuftoti "'' : was the s [ute nfl 1'-A I added to the
resingel, V4 wa the vtlunir- f lisa rsItl gel. itif I sat'. tin
elution factor for each mct.il ultecnncentratinnitlte mciii
measured by Di t'.i
'hiravailahlc ' watem coliL-entralion) was diaterintited If in tile following equation.
sap
Skeletal Defortaliko. Illoasotty I. Rli'er Water [xtI'acls.
Water samples wear cillect,-0 from tier siudi locations
during the summer ti 21012, Sampling sites tnclttded two
Newberg locations I NP- N :15 1551; ', W 122 7oil 12 and Al
N 15 Ifi 117. 05 122 55,1121, lthtemttitaitl i-tire WI-. N
15 05 117W 123 021>55 arid Comtiis CV N i-i :323387',
\V 121 t5,422 I I tneachsamplthgilui-, smnitiiicswil t' collected
frotn CV utri tite 1 the oLlser tho-- s.ttttpliug liticatititis At
each site, tinee 20-f Dab sampie: were c Ilecied in st,uttiess
steel cl,nuantv-rs, Samples sane typE-mills' ci heeled at a depth
,
Jt\- i)ii)
wltcreAçwastitc titti-kitess ofihedillusive gel sf33 tumi Plus
the thickness 'tithe filter nietnbrane 10.1; junti, I) was the
dlffuslt.itj coefficient liii end in the gel tias depioun cot
i. t i ctni I
time. and A was lime expisur area i.
nIsI.stiI INtl.', In Nitilliet ii Plkcniliin,wt ti iti Il'stte.
Notthern piketuitittow I
cuw-:lasi 0 -is the sfiecies cli ,sen
foraniivsisoftttattriit irtaisier .iPCPs. thee crc Alittttdattt
at both stud lc.catiotts, reitmtiveiv easy in c Let, reach
moderately large sizes, a tid have large nmunie r Idefurmiltes
In the Newberg region lu.l.Adults we: e collected front
Ntiwberg iX 15 ILIaC, W la T..i'1:l and (irval1is IN
442820,W 123 1.1.751 iligitre I in -lav-- iiine2iiU2 using
a combination it hok and line and ci,.ctr.fisliittg and
transported to rite iaboratiry it Ice. \Vi-t'vcigiiis r,tnged
froni 375 to 975g. and there was ii 'ignil'ic:ttttdllietulLotn
the nican SeCI weight of the fish eoliecteJ from tic
siudy
sites. Ovajian tIssue and assicialed cvtcs iSIL ieitiiiyed
fritin giavid female, using eletin, sail vent-rinsed, dAwi'ti'on
ml oteade strean, i IN-c go using a Zvmark 'Itirhi 'yap tI 'the
p '.aleoi cotleeutr:ites were tratisferred to autuber glass vials
iii P( )Ps. Tv;cn iv- 'iii ci tint i na led peitteides were iluanil I ted
bvgaschrumati:igraphv ivitli cC .1 F 'Ii Capture d&iiCtji.tii CICI
lt(t)irIc corilitig I Lit tnL-llii ,'icI:l..\ itll)t3) lii stuutiry,
Portlatil Liii .1 saentv-eight piivhloiutatcd highenvi iPCBi
coutgetlt'rs ore qutittlilied by 1.11 PCI) acciiaiiitg to i.PA
method 11(1112 (r)Dt-çt lahorautre, Portlan dt tO
.'tdtli lionauly,
CrtlicefltrattOt)S 00 seven polechthirinated diLuni.o-p-dioxin
IN'[fl)i congenc'rs anti In pulvchlorinated dibeuzofuruns
(II P1st uco' guam'
hi ht,h tcsuintion (A ("Is
Analytical, LirtilsIt Criliinihjti, Canadal, Method detection
limits \ifll.s fur cltl.rinafed pectiudes and PC1IS ranged
from 2.5 ci 351 /1g. kg wet sat. \ll)Ls fot PCDD and PI73Es
ranged itoni ft I tO ii.t 5 rig-Kg iset Vt.
PlvcovarLtiv ussue;iiei-te samples Leach Iii ni aseparale
fishi were attalc'zetl per stttdv area. hr statistical analysis
and pli:ittlng of IIUrcS, o.incentratiouis bet-ac the metharl
repi.trting limit IMRIi or d.-iectlun Until were as-,
ted to be
equal to one-half of the Until. When assuu ipitons of'
patansattic statistics stawe met, i-tests were used to test fir
differences among sitoly sites. KulinogorovStttlrtiiivs test
was used in cases that parametric assttntplions seeje it
met.
.-tiltilysls t,i PoP, In Sedinient. 1,1 mb samples il surhcial
sediment were collected -fr in t-wberg and c5r',aihis sites
In 21302, three samples were collected a) Newberg locattn
34
mm DVB-pholiic lijiloseed t't a [tvil-phiillc solid-phase
extractioti disk illakct hutid aspeedisk 8072-126, 8)tlit1-05L, I 1,
Baker, Phiiltpsbumg, Nil, 1-low titles iscre 15-50 titt,"ittin,
following extraction, the disks owe Ailed ttnder cactituhit
rtnd stored in airtight o m isittt'rs at 2) 'C met night. To
prepare bioassay eunc-ntrtite-s, each disk was cluted three
times with 5 ml, of nieth tn' 1. Stethantii elucnts wet,' dttd
tsratotv Practice-a-
ci-ilified atmletical laisiraloiies hr quanhifk'ttuin of a range
I
The (10 1 of outer ci illeeted at etti'hi site' trIplicate 20 I.
sampiesi wasdisided mItt live 12 l_stths:ttitpit-'slor extraction.
Each suiistnmplt seas liltered tinder vocuutrt through a 5-0-
i'v passing thrnngh to ci .ltutm ii N-aaSl ). For eltell lte, di ictl
nteiltanol elueniswere' pi Ted and t's-aporatd-d -tel :: tnt. ttndt'r
until extracted.
1
t etnoved) tindere.ater, in all cast's, ciii m-ciuons were made at
least 311 cm I-eS ',' tile curfitce titid at least :io cm above- the
sedintent, Stinpis- i-xtractt'tn wits criti:pk-red within 953 Ii of
sample couleLtulil.
C
tools: j.tl aced into certified l-Cliemn jars: LIlA stored at
saitiples here 'ILIIIYed to I lb 1.
of -A na, and :tnt,tinersieere opened and sealed tall aIr
ENJtRONt,IENTALaCIENCE & TEcHNoLOGY . VOL. 35, NO. 10. 2005
and shred it ----------uttmii used Ii bioassay.
tithi ugh nut tic tihatishive c tnultuntethiitl procedttres
designed fiii lIt,: e'str:tcthaut and analysts of a wide range of
Org,hLtui- din iantmnauits in sttri ace u alto- 14'. the extraction
poiecdure ilescriicil above was designed to capture it
-cnllIcattt cross secttott 0! disotili-ed organic contamtnatits
'Ii g k----t iii the rilige til 1-7p seitht a res-ttlting tnetlumintl
CII uli'd-titf ate 'imitable Itt the' in a fathead minnow biotsstn'.
I tsittg the extrar-n- ifl in ie'etltlrc described aboi s' i','iIlt ethyl
avetat,- is the eluvrit. ,ilss->lvedrcstdues of over 101) currenl-
use pesLic ides and tufts tare been recovered and analyzed
lie etipildoy 1115 MS Ihsemoko anti Simcittic-lt, pers. intil coin-
ntunicatti,ni. In assess extraction i'ft'icience. ri-i-sr water
collected at the Ct' star was fortified at hulL'S llg.'l. with
chltuullvtitus log K,,,
4,7i, a weii-lonau'n \Viiiantette Ilivet
contanunanr, Ethyl accEde extracts Seed' tutiih'ieul by (7,'
MS usttag the method oi itsenko and eintonieh, iverage
receverv startdartl deviat bitt was UI i .5 it 00
Fathead ninticns's iJ /lalii:t'itl,ci less tlniio2 I hpmmt-hatch
i
weii'ol:itaiyedlroni Cht-'sapi-.ikc' t:ttilttres lInes. VAI. 1_at's-al
fatltead mintoows F11s1: 24 lOt it past-li:-tteit , seem e rtndriittiv
assign-ti ti lt){l-mt hemikets contaiitittg 111,1 uttt of uk-chlorittated tap water I this i. Each bcsiki'r seas slicked witlt it
:10 l.treal II tM Eeakt-t se-crc then randuwir assigned let tile
of eight I reahmhhi:nl groups I reaitnent gt outs for the stttd
V er enijtj'ul till", _llt'l ml ii dto ) soli Lilt Lottirol 150 0 (1 ,°,
139
Me011 In dlwt; fiX-, IX-, and 1X-Corvahis: OX-. IX-, and 1X-
Irish were delis em i'd iii. 3-7 day old and were InItially fed
NP AL cit WI. :X. IX. and IX
paraitt'dmmmtt ettmlmtimes umitil ab itt 1)1-14 days old, thenwere
switched curt mitixcure ct brine sltrimttp Illltllrthlti 1CM. i.lrine
pescirt the vciumL: i the
apprpriatc:slruct thcsolved in 200 ml. dlii Li. provIde a
conceotralioct erlun aleni tollS I. Ii JO. dlii! I lf,. respeci v
01 river waler cincin traiton Lit the curs et s ci ntit uctt is,
assuming 1006 reel series. Mitliatti 1 tess ddcd ti. eadi
1
the 4X and ix lrcrittnelii
uclt that the total
Me..)!!
idirititp rind In cwe-drr',l .spiruliitrtmlgrtt iAIgit' 13'asti__kfler
rrtu1 )-i
fish
',-cue titc'ti ted TclirsSlttt flake hod
urcirri Sales, Blaekslsmtrg. \\i.
Liii, 0 05! tell: sort us lCerc ci 'Ilected Irrim the \ewlterg
concentralion was equierilet ii (i chat 01 the L&' reutlItdHIC
and Sc .0dFt1IV CidCl a k { liii test si.luti II was rriiereed
dailyby drawing the iriltulit d en to Iii ri. rind addiiitr
100 ml. of fresh tet solittin cuntatniog ni.ininiil coilce,ltru-
rtrt',t ligiare Ii Irons iutie to .kicgust 21.ttiR. Cc'rcrtrlae consistent
wIth those dcscmlbed he Niettil acts! Macs ItO, ipigure 2a1
tlonsofcxtracr, iii I:enr or both:! ho locauin .1 oalt heLr
on the exposure hncit was assigned rruidinlv titI ill
beakers were aeratci thtrtnghout the 0-epositre iluittl ir.
tnrmmmlnmssein studies, larval frmthertri ni intl uws
After 5 days of exposuic. survivingtish were entitled itid
transferred 10 I -L plastic containers [or gru-ilt i -d tb
25-30 post-hatch. During grow-out. itsit seer iiritttainied
In dtw supplied from a flow-through system. T0r.iiigh err
both exposure and grow-nut writet lent per,ttui
err
maintained at 21-26 C phulipetlel was Is Ii li)hi.
core Itars'ested fiotn inrliviulurtl tiall be holding snails itt
tsiluIi eiitm 2.1-well tissue cttit tire pit 's Iti 2 inc_ui water, For
1 varvirtg age
15110 ii were exptmed Ii kiti'';n 'liii entice rhts ofcercarlae
ci nil iSs ate! Ijtllt,tI I nials with s'erv ytttmttg fish testtlisd
in ItigIt tiiitrtilmly In e'xllisstd [kit able Ic
lit-i deoce itt tnlcctton, t'crtehtal defurmittt ms and associatits of wortats with dirtorim I irrnr seas determined by
exritiiiltrtt ho ofwlaolc', pteserved isil that score cleared with
ii'psin rind stained with with allan joe and olierrmn-red S
;iii. Fish were collecrett rut ehtimci
(I Ii
daik, and FilM were fed S/nrarnr.l )Algrtc Fern I.:trthrirre.
Petaitima, c/si cult-c daily and brirte shriuip n:ritpltl t SI
urine Shrimp. Ogden UT rice drill., Ltisseiived oxygen plc
ainnionia, turl ttiuritr' were rraoniLured daily.
Atthe end ot Iltegrw-iulperiud, fishitona each cuntaitter
were te-ansferrird 1 a - cm-diameter plastic tube with [toe
mesh at one end PVi Insert), The etictre hatch if live fisit
was immersed in a (1.2... calcein Siptita C-iii17: St. Louts,
Wit sitctin pl 7)1, stdtLtcd lit to mitt . trmiits[etrd to
clean teater liii iii olin I. distrilmi, sit! mIro euthanjzod hr
irtqui1, AigenI.
ltetli.nrcid V.\ I ro h:tnizeil specinhsits were inmrnedialely
exaciticted hs lire i issetiri tlttcrr seupy usmg a Leica MZFI.l Ii
intmurrsiun in ri 20)1 nuil Lsohmtii.n ut M's-222
dissecurri ntierilsdi..pe ithiutit's rtitd Stout. liellevue, WA
equipp'rl with rt it ercitrv snip and fluot escein.igrecn
fluorescence l.rnletn ititot. Cakcin staining allows fur dtrect
vlsutticzatiort of calcified skeleiai slrimctitres Ii). Fach specimen was eLmitned fur skeietril del entities, inriuiiicig smut-
sls lordosk, liwed vcrtchrae, compressed centia, cr1 raur
missing sinuos, etc. Seri'enitmg ofst'v'r il hundred fish is part
of assay ds'vJopiitetir rintirnied that all these types of
deforntilies ...crc detectable he this method, Vertebral
developitietilsrasrtls:swreduo rmscaheuft-5usingaeriteria
duilnid li this tuth'. Digital imagEs of each fish and closeups ol delurmiltes. if detected, were captured rtnd archived
usinglmagerrut puts t 3.i i.5redlan tnrnoiicc, silversprings,
MD). in scene cases. exiimttictaiiins were spread irer 2-3 d.
ItepIiCttes exsunincii erich day were selected rttwlunily.
Survival In cite nj of crposurc d pusc-hrttcit rtrvivrtl
toexaminatlon 21:- nd pust-ltrttc)r,attil pr-rcurtinf situ tug
fish whit a keietrtl (letoemile were del :1! iii I jr each
replicate. Deveinpinetital SI mc disleibuti irs ci e determined fir each trcetmnwtil. (tue-way analysts .1 vtriattL.....is
used. to test kic differences in survival r iticietetiec of
deformities alitotig Ireattrii'tsts. 'i i enpriritmel nc Km itskaiiWallis Lest....ii rrink: was iit-i1 i. test U e,rlcnemil-tclrmtcrt
dilitirences in c!es'eh pnmecictl s Iv disltibutione.
Skelcial Iie1i.i'iiilths ItLias.sav Il_I xposuretnt;iopltsiffos
ddith'tcc Cerearlac. rhrmrrcicrizrtti mt of prtrasite association
with vertebral drtoututies iii Wlilamette Ill--er 1ihes was
based on exrtlttittati,mm of iii stutogicrti seclions of fotmalittpreserved fudi ,is well -is whole mlitictts if Irvlisin-ckai ed
ii Ti) driv', ptmstex-
Psili' ttli'riitillslt were placid icc rt Pert dish, coveted ssitic
'-'ccci tt roil ex:imuincd at 25 sr Ii
l;tshi were also ev..ilurmte'd
hg radirprrphv, as desctibeml liv %Iartl....I al, 1)4).
ReuIts and Discussion
1I'formlly inrids lit VflIriiaie1te RIt'el' libili. One difficulty
assiciated whir the use of [isis skoltal dcfortartttes as a
bimntutnituring toil is cite ittek-. of .htitiurinrttlomi on normai
Isaekgrt'und deformity rates One stttetv In salcnotalds suggester! thaI 2-- 5r' ion' he a n'iiitrtl limickgr'imndrate In wild
p ptiirtti mis s ticwer Cr, it is tmiiclr'rir tolltecher deformity
rates differ rttniing species r.riii' ii!. hiolttlrtthOtts ssiihiti
ratrs are itsually
hiiottinit.ttiisg rtpptiirrehes b,tscd oii skeletal
species. l!et'rtusc backgrur mitci.l dcli itO
utikmin'e'rt.
dm'iirntill..c relvi ii Letitllirrth crsprttirml cotliltanisotts, ouch as
s-ear ms vent cltniti,mies, ir ci etlpntns-.otms hst'sce'ti locations with
slitmilar habitat, ehitttiIc, etc. itt t\itluti'ie'ltc illvcr bisla, the
11 jrteked go 'graphic disipari i- its lreqttencs if skeletal delorinntics suggested oOzed ' 'bLots iii Neiehcrg aitd Wheatl,ttirl i-u I
S)ttt 2lti)2--2uii.i_t
:siiit', is'ue citliseSilt wsih pres-liuits
sntiltes iItii rep rt'il t nrc Itor lctciilcncr cf sk'k'tai cti'furittities In IVi lI,tnieite' Ills-er fish front Nc's-berg atid \Vhemttlattd
Few rektmive ci U.lrv,uliis )J/ !l.tttsctg the live species
rn si ettimi liii 'tmiv satutp led. pt cent ireqtmettcv if dcl ,rcnt lies
torts grttei all" 2-- tunics greater it Newberg rind \Vhcalland
iii rr unit rtt t it ratlts l'rmhk- Ii, liii' univ exception torts the
l:im ge-scat' stt.'k,'m if rtrluJ.'Imo tiSl,''i'uule'f,5r1.i , s-;lttelt torn mitt,
only c'rit snytnid of ihe fne twist cirmimnirtiv collected kIte',
\mti.ttg lime cvpnctids. iuentn dcliitiititu' lurstis were usiiall
sigimitteantiv lowet for lTurrnlhns fish rho fr fish frirtit
\VIre,ucland Ferryir Nes'berg lJtrble I Thr'-m were tilt obvious
geographIc or lutf'4irit iille-renee-s tim at explained the differ-
etices observed i Irti. merrill, bliutttniti.'ritsg il skeletal
deformities in fish collected at mhfferent I icatii.urns along the
Willntmiiette lth'cr itt 2002-- 2ei;.t sttpported the clrrclrmsmort
that fish ppulati its ttertr Xs'scberg and Wheatland Fctmv
were note likely or hrilyc skeletal defom httes than fish irons
Cumvaihis. Spit Itmsl ricrtl snmitipht's front inttsetmm collections
cimtcuirtttlugit pr crnidrml tloirniitv loath ttt,33- 1 4 perfish)
Itt liii) mt rscv:li.-tg amol WIce,itlattd Fcrr-, a Iossr load itt
alcian blue cold aiiaarirtrrJS-viained Ilsit i IT. The tnthosls
1. I/i rut \simeritlrictd 1-err., utnd mi lower lied upstt'eant
ol Cors'rulhis ict 15)7 Ii 12 .1 )1 These ltist'rlcctl data do trot
andstatisticmti anribsis used for theparastle chtarrtctcntzannmt
11111)
were reported elsetisere 47).
1or iabormttorr tr'jlsrrrlssittti stmtdtes, laltatrs-reared
[atIic-td ntinnnws va'rcIir,.iitied lenin Cheastpealrc i :ultttrcs
[-layes, \3I. Ulsit were lielii itt dt'chui'rimiated tap wrtter i23-21
C) to ensure ttnoxpised fish did not become hrth'cted I-wit
were maintaittedin stril re is rime nquarlawlih htolt.iglcal illtcrs
11152
In dlstIttgumsit slung three possibilitIes: lii site
,.-rtnirition. and the range ot sciriation we delict Is normal; 12)
talc's at 0t i-allis represetti time hackgrtamil. utnd Newb.erg
rates rice eli'vtic-d: rtt 0
rtmc'srit Net' htirg represent the
backgtuund, rititi t.;itvrillis liii ale' depressed.
1
Wmiter Qtimilli v (.Iirirrii'ieri/,ithsn. \cutmmiottiil. nitrmtie., piJ
tetstpe'rature dissi lye! ox'gets, oxldrtttve ceducrtsutspoterttlal.,
VOL. 35, tiC, tO. lOtS) ENVtfiOtIMEntTAL 3c,iESCE & TECJINULOCY. a&aa
140
L..
FIGURE 2. A. donicz,s infections in laboratoty-reared fathead miiinows A. Pa,aplophocioco:is cercaria unto F. neos used in exposure
trials, Bar . 50 pot. 8f. Metacercariae lairowsI associated with skeletal delorinities in cleated fish. Bar 200 pin. B. Metacercariae
iii surrounded by liony prolilration at base of a vetlehra C. Metacetcatia in reyion of severe lorilosis. 0. Dysplastic sertebtae and lordosis
a; site of infection. E. Meracercariae associated with lesions: 1 and 3, no sigirificant changes; 2, dyspiastic and broken spines: 4, severe
lordosis; 5, metacercariae in base of anal fin with is changes.
TABLE I. Frequency of Occintetice of Piecaudal Deformities and Average Delonirity
oaitv mi the Five Species fiosi Coiurnoiily
Collected horn Three Willaritetre Rivet Study Areas in 20022003
Ptydhedosoro.qorrenais,
northern pikriminnow
P I m/'s'rao Laura rtus
redskIn shiner
catosromous rnacrocheiis,,a.
iarçiescale sucker
23.6
0.37
14 2
024 <-0029 8
14.8
0.21 . 0016, A
1394
Mylocheilua c.aurinuo,
pea inmith
Acrc ra lj 'i(uraceue
chistslmoutir
14.1
0.20 . 0.032, AS
305
24.2
0.34 a. 0.033, B
30 6
070
2h-
r1
0 01
Off'
Nt
6.9
0.09 ± 0.01, B
928
C
ij 33
938 B
4
17.3
0.22
0080, A
127
Off
DL°
0.016, A
Corvallis
Whearland Ferry
Newtrery pool
species
2314
c
22.8
0,35
1
U
21.3
0.34
20
0 O'
0.021, A
1205
001
os
1001
0.1 11, A
47
442
9,4
0.10 a 0.038. A
96
14
0 00 C
251
" U 10
B
lOo
1
U1
Fiequsncs' :4 'wcurrerics at precauclal ciefc'rinitiss. Deloriiiity load.: ritiniher of detornii cnte9orues present per individijal; newt ± SE (SE
is incii'oiclual ratherthan poc'lsct(. A.B.0 indicate siyniticant difference :etn'sYa rite. p .c 5,95/ brired rn Bonfrroni multiple ranys toot. 0 Carrtplt
sire.
and specific conductance data were collected hourly during
all 21-d sampling events. At each station, some parameters
showed strong temporal and spatial variation, while othei's
did not. Diurnal temperature variation was greater at the
Corvallis sites ii 2 'Ci, than at Newboog CI C or level.
Temperature patterns were the sonic for both wars and worn'
generally 12 ± 1 C In May and rose to ".22C :b 2 'C by the
have bec'n linked to skeletal defomuitlt'o in stickers 125-261.
bitt we are not aware of ank' reports that link p11 7,2-8.11
cuiiditions to skeletal det'orntities in fish,
'the oxidation reduction poieutiai cOBl'i probe tended to
tirill tiler abotti 7 tO days of depk'ivntirut. Sitiec till deployI iir'ii lower e 21 days. data alter 7 c1ar went' exclu tIed from
Ihe analysts. OiiPwas consLsteittivlowerat the
ewbergsItes.
end of the sampling period. Maimum Pt! range doting 21
It, usually tn late May to early June was L2 to 711 at the
as cotnparn'd to the Corvallis sites, The difference ranged
rum ' i0'y.toa factnrof2.Thure was no apparent rteasonalitv
Newberg sites rind 7.2 to liii at the Corvallissttev:t'hn'sefarge
diurnal p1-I changes were seen in both years. At all sites,
ii the Corvallis sires and liii It' di ffert'iic e between 211)2 arid
21303.The[e wassonte evIdence that the OflPlncreasedduring
therewere sinai! decreases in pit from 21)02 to 2003. Nlglittinre
tits' season and differed among tears at the Newberg sites.
pus were similar, but the daytime pit showed a strong
Tljr' (188 value is a direct reading of the activIty of oxidizing
geographic diffcrence, sdth the Corvallis sites often l
and reducing agents in the water, as they correspond to
pu
wilts higher than the Newbergsltc's. Low pH conditions l
3500 EN VIRONMENT.AL OCIENCE & TECHNOLOGY/VOL 30, NO. tO, 2506
oxi dat ion redsrrtiun reactions 1521. In general, the Corvallis
141
TABLE 2. Meai Coinennations n)I) ol Cloatailable Orgaiucs Estimated Imoin Coiiceutmaiioiis Accuiiiiilated in Passive Sampling
Devices Exposeil lot 21 d at Two Sites (2 locations pet site) along time Willainene Iliver'
Cotvlrn
Nowberq pool
1PAH"
3.17 2 147
nrithracenu"
1.32 0 0.92
plinnthrnu
1.22
1.
('.722
i
('.6(0
'.hlrpyritrs
0.94
,, 0 1 97
:641:1)2
0.61:00.07
9(1 1
(.923
('IS.
0 .0 13 .. 0. (19.
((:74
ii5
".6'
6'
:1.049
roil
0.01:
..o 0.6)2
0 .323
61,900
0.023
0.007
1
3:19
(ll,,l.:Irinn
.
'
(1
0.43 .t 0.12
.46'
OPT
p,'." DOT'
1.72
((33 ±0.27
0.9')
10
2003
0.34
2.01
:,"3
0.53
flit ornFnh1uII)-"
1PCEI1'
2007
2903
2002
0.609
NA
('.74
or,
61.011 3. 6.202
ariA
(1.021
00 (.33
NA
'7.01
('.606
0.) 1017.764
':625 0.769
,'iIli ':":'ii':'ritIiti'..Io. -' dnluLicin Iin'iit not nh...'.',ii. C",., SuI:.I'....l'tjnu Irifol' 101011 lou 'ornpk'L. Ii'l .1 nrioIti.'r. Ojnificnnt
diffornnct L),''nuwl silos :5111 sooir. Oiauiificnjil clIffururlcl' lOIS, .011
20:3 :1113, "tql'li{lcOl'lt ffnrsncu l:01'.,l".sfl nitu's. 7(0311(3.
Tnrtj-ot rtnnl'11.',.t.
TABLE 3. Concentratloims of Cldonnated Pesticides, Polychl ominated Bijdi en yl s, P olychlominaleil Dihenzo-p -diositi s and
Polychiorinateil Di hetioImnans Dete cle ml in Oocyt Ovamy Tissue hum Nomthietmi P ikenmmummow )Ptychochemlus orgeotiensmsl
Collected from rJewhiemg Pool (NP) and Corvallis (CV) Study Sites
SE (tig("
'
cornpolntd
mediiut 015/50'
NP
atidrin
4,4L000
4,4'DDE
P50612,43
3234 i' 1.62
3.1:3 ± 1.34
4(00
.
3.2')
12.4
1.74
NP
CV
P
'1.60
1.62
(1.191
1.69
35.0
1.60
1.62
3,171
31.0
7.70
0.942
0.144
1.69
1,65
1.62
1.62
02399
P5018 12.2',91
P00191 12,2'.4,O,E.i
(1,7
P0611') 123 3'4''3l
('.49;
1.65
('.96
1.65
1.65
4.20
1.65
4.16
PC:E.111:l2.3'.4 401
P5.0130122 344 0']
2.43'
2.3:1
F...E1 l,l2244 r
4
TE0ipanp,sI
0.04 i
1.27
A
(01:74
0,671
3974
0.163
0.999
1232
1.05
0.67
0.99
(1.213
0 .46' 3
i3J'(t soit '1.1
Fur Ifs purposes of cnlcitlstin,j rt'twns, nwrhnria. and statiotics, ON I blot '.. '.vors as'.uniud to, On 51111)4 Ii) '2 tli ninililod d10nctiur'i loOt. All
C nawttrati 15 rn(YI1l Ill 13 01 '
Irillate sa 1155
1 "a ," I TOO 'bit 9 ,ii I ,. rtd a
t
in Ii
hl us 5511 'Ir mn lj,tn
I
than the MDL.
I
TABLE 4. kmcideiice ot Veitehi oh C eloitmimiles and Wetac.eicam iae in Fathe ad Minnows (Pimephiales piomoelas) Eapused to Cetcamia e
ol .4pophallus doniczis
eortcti of
ettpouure
triI
oc,
ae ol
ettponwe
ce,-eeiia&iith
yn(
tlaa
titiwittitien
pleoposie
mititlisi
when exemitteil
exataeti
09
90
11
1
30
8
10
0
)4
0
19
d
Th7
14
20
0
8
76'
18
2
30
30
0
4
S
31)
4090
0
5
7(1
17
24
70
"Ii
14
1124
71)
a:oo,l
total
t.:.t.tl c.c.nti'l'
21
19
70
99
0
12
4
1:
1.196'
I
1
pannaitea. N
1.0
9:10(99'
911 /82)
I o 14
3,
0
0 1'S'))
1
1
1
i'23'.'l.'
'awLs osic lItre cixidizing, orh':,s iuduottg. than Noa'lcrg
very (1 uil.i: .1 tb1 & 3.t'v;iLl Is
I
1
0
04
91
4
0
auseciated with
0
1
I
dc,
NA
NA
0
2027
NA
171' ion'
0
12
0
(1
(1
131403' 14:14 /100)
ns'aLtirs. ('iFOP I'. known LI litllu'ti'' ttbl'ui,I.lbaI gruvo'Jt. bitt it
'is not clear wh1h er lie dill ci cot.' (It 03)111 4'survcd sci old
make' Nunclit'rgfish rn ru vulni'j ,ibk' 10 II1l'L'tl' In liv miii ulii,il
agents ot' mcnre stuiuptilile I''. ilcl'o'tntiti''.
Specific condue't'isiiv (SI :
IIIIIIIIthIItCC
911 232)
0
iitfesied
%
911 (72)
7
10
12
1
'.
worms
anoeiaIed with
dafermitiea. N
delsottetl
4.5
40
0
2.9
'3
314
NA
31.33231'
4'
'0 12(971
NA
3064 iE'31
15 08 11:5
4
6'
°:
17
NA
60)
9
int'i'easi' in :ul'Itnl''nibt l'nitt 0.113 10 i.29 mg/i. was measured
at III., lIt siLC'n. 'aitil t3i'vaIIIs g'iwt'ltlIv havinglaiglier ammonia
than \1't'bei'g. '1111' niU'ati" glob' wan ott' robust. In 201)2,
dciii gc'Itr'rallv ,ii'rttrted within 2.1 Ii of dc'pli.'vtnrn&. In 2003,
Ihepruho l'ai]cdwllhlna fu;'h"strsal' di'plusntuttt.i'helimited
data itIdlilttcd that nitrate Increased frito ,luv to Jttiv. and
andNt'v.'hrrgnitts. with hrltllsltl01119 .1 sJilfhI iue'i''aae it'' in
inlay tci July. The SI' pIIl'r"rn win sitn,l.iu (si built 'i'ItS. 'Fit"
dissolved oxygen II it'll 11:111cm 'so,. 1itiiiliit 111 1,11th itt'5. A
diurnal pattern wts'tpp:Irunt, u 1 'a sliglI I 1ls't'rl'On' in DO
concetitrath Its wore ltbphi'r at 11w 7'wl.t'i'gn1 15,115 c'iiugarcd
was seen frcim Moot,, lull' In bath 2002 and 2(111.1, A seasonal
cmadtwu'ity slurs hikclv causes 0 the diflbre'itt dcli nitty
to thu Curvallis silcs...11 WillIe. O'ateI' tiiililv Ili1)nil'oring
guI 'sid1'l ti. ci inpelhi tip i'vldt'nco to Sllggl'nt that dilk't't'twt's
It't. ttl.ttt'tCtIt CIlLic'itt 101bl''Its, 111 I. te'mprruiurc'. I >0. or Spc'LIlie
VOt. 39, NO. 19. 2905 EN"IHONtlENTAL SiltricE
TECHNl3L0G'i'
3501
142
loads observed at
'wberg vet sos Corvallis, hut futiher
itivestigatlonofa p itrIellnkbctv,ertn lltPdifientrnccsand
susccptllilin to ii if ret i,-ii clay be
rrantrd.
ltlivalltdtlt' ull tiltiants. J5?.uiCt51i'. tvfl2ttti lit/rn-
ciii?ti.4!Ls. ri at bit zn ailable Pt tic
v. re it sc at alt
locations and for all sampling events igene utile I iigl .1.
the 10 PAils uwistired, 13 PAItttccere below ileteetlin limits
p ., 151)15; 2003 p .. 0110.t. Itowevee, the' hi tttvat able
ctuncentt etuons tuf diel.drin were very tow, It 21 tg.'L, and
Iltete was urn significant difference I.tetwct'n vials iNeteberg
ii') t; Cuevai)i- p
011113, 'table 21. 'I'he diekhaia
conC'entrat)oiis iinwct ed wire anoLuad 2, tilt-fold Lx'low time
ireshscaierCi.t',ui ii.utS6og,i. ).Sii and tire well hr'lowthotse.
SO. \Vc' are nut
generally thoiigtst ta be Susie to tts,h
N 0.1 ng/Lt in J' '112, and 11) PA! Is nere belt sc iii 20.2.. I'hrce
aware cf any repair lhitkirtg below nato grani-per-Iiter
PAIlsphenaatltrciw. fluorantlien i'. and iii hi racttewCi e
detected at sites ut 2002 atid 1'
At ii
.rvallis sttet
concentrations a! dirtdutn to ck'hc'ttil Jet urutuities,
Chlurpvrhflts seas the utnit sgtitplt sphaie pesticide
detected, Dini nthoate, diazinoti , anti aitutphttts-ntethyl were'
below dementiout limits ii all Silt's itur till sautpling events
idetci'ti itt bum lie were cci! twa nil at 2. 2. and 2 nghl.,
respt....livelyt. lii 1111.1:',, Ihi' t'ctintzited, biivav;thl,ihlc. water
ctncc' ntrauitn for rhl'irpvrifns a'.'ergnd 0.71
(I St lit
Corvallis ,itd 1:21
135 up;!. it t",''lterg If attic 2', 't'hszte
was little dmlfeeenre between the -a cs ill I Li iii' ,titd Jtth', but
there was .0 cue dhifcinit cc hctwr tit the' Sites lit ttty, with
1
lahensiithrcns' utd atuhraee it 1 tnt' equath abundant In
20112, whereas tittoranflieni' was cunewhat Iss abundant
(Table 21. 0! the three CU is tkiecic'd at the Newbtrg cite
in 2002. phenantlsteni' was thme itmt,.t abundant çl'ahle 2'. In
2003, anthract'ne see'. oust alattudant at Curvaflic, and
phenauzdu me was in '.1 ,ihitttdaui at Newlstzr/r 1 the I'
ltidi1dttal l)[O.tV1LilthIt'
U Is, Jfl 21:02, the Corral Ii', cites
cnnsittt'ntiy hd higher total Psi I 21'Alll cttnceitlralions. as
cttmparsd la the 'lt''t'tt''i p siim- 'fabh' 21 lIt' and ipt PAl I
.:.t.2 ugh. ti Liyallts, whir ta' the Nt'sebetg
siteshad 2PM I ciiticentraiions in 2002 of tb ti! 2 ng L In
isa 2002 v..is
2003, this ptnit'rit was again upheld iTahic i'. The Corvallis
stations 11 raid 21 had tAt Is of:) aid 22 ugh. tecpcUvei
the Newberg statints it and 2 had l'A1ts of 2 OgiI_
Phenanthrsttss produces spi it. 1 cur-el Ott' in erbiafish cmboos at contcuir,tuistns near smiler calurtuirn 1.25 alp..'1..1
(53. With low cotts-enlr,utions detected ii ho iii ci its. I 'At Is
werenntconsidc'rc iii lie likely contribut i$ the ihitieri'ttce
in deformity Irads assuriateci wtih the Iwtl areas.
Po!ve!ih.,iniitet! l.ztt):a't:'/.s Pl.M.s: PCB analysts lot this
etudvwas based on a sritgi'iini-speclllc approach; however,
concenteations of all Cut igennus set-tm quite litw, so interprelation of results 1/ ti.ised in t ltd Ii 1! c iicentratlons.
The total hioavallable 'Ct', iritcent t:ol ns were getintmtily
vecylow, <003 ngL. at all shies, and nianv sites mute below
detection limits 101101 tiguLt 1.'ihbc.ii. l)uring2't.12 ,ind 2t.ui
toralbicaavallablei'Cilswvrc gencrahl'cgietsit'r at the \rwht'rg
sites h'rable 2), f1ows''r, since tnt st a! the data 'mere below
or near detection limits. ii teas hiflictil 1 5 ii raw ani fIrm
concttisianis, POt roncentratirns were a [proximately 500fold lower than the clii roe anihsieni scaler qtiztlitr ci iterla,
CCC) of{i.ttI4pg/L .5/1 and liter lid rut re.idll explain the
difference in cieftinnily loads tin op sites.
Pect'ridt's The bictavatiahie 21 ill stint oft' p-DDT,p,1CODD, and i'.j)'-DDEj COnir'lllr,tUuils welt' how igeneraily
<0.07 np'!.) at all sites in 2' '12 and Air's . [able 2/. 2Ltllt
coflcefltratii:ittsws're'-.- 10-flit I-mS te 11w..u'shwatet CCC.
(LOU! sg/l. i.S.O. The dilts'rc'ni-i's ci 31 t)f between estterg
nd Corvallis slit's 201,2 to ... lit e iii it dOt;
0.005)
weee mutt sigittticztnt lIable 2. tntett,,,i,ti,tt ditimi cures in
.
'rIO Nev;hvrg;
ltD I' sans rtgstalinttc were itt-I sigiuitictitl it,
fir... 0,2-I Cuirvallid. In 21.012, tilt [lIlt' pnufi2: toisdiiiiititd
b tl,1.t-t000, (ollowel liv lit itt raid l'it)T lahhe S ,m,t;'iithsl
be expected from alder lu:ptisits. I iu,stdvrr, ii, S''2, 0017
domino Lcd, folluteed liv iii 13) at) 1 'III table 21, DOt.) and
D011 cr,Ltcs'ttiraiiutis d'iei'ieil tit \m-,'herii SI icc in 2112 and
200.3 were not sigiiitit'aritiv tihlereni p
kilo DDE
--
concenirationshutii':il 101 a rtci'ntrttiailsat i .,',-.tlll'ssltes
Increased slgnili,tattllv hetweeit dtt.i2 ttl hull p (hilt!
DDE,; t
.1 sn.oi . \iets tiler cu tscenitati' as at 2ewhwg
-
did not hticicase cigniticatiuly beimu'enii 21,12 raid 201%) 1)
I; Table di, but iniriti biozivallable DOT dtncted at Corvallis
increased .4-fold up
(,0q4; Table 2i, The cause of the
Increased pp-DO...concentration was nut clear, but the
results suggest possible new iiiptits or sedintent disruption
remobilizing DOT, Eteerall, the crrncentration dibfc'rences
observed were vet" sttsat t '-'51.00(3 ng/Li, so cuitrlurlons
should be drawn prudent lv,
Dieldrin cotwetttratiu,t is ccii' slightly higher at the Newberg SItes, as compared to the Conallis sites 3 able 2; 2002
3502 EttVtROt'ISIttITAL CCiENCE &TECHNOLcGY
'CDL. 15, Nc. tO. 2005
h
1
-hih.rjuvrlfus concenlittuu,utus at time' Nu'tein'rg slit's bight....than
ut hut' i :nurvziihs sites, however, time cli fti'ne'tict' meOs 1101
significant p - it SIt, 'lii' luioavaiiablc' c'hlurpca'ifius t'inceuiti'atiuns tabsciveil in this studs- were below 11w' chronIc
aquatic life cetterla ciflltlluplaisct,..elllnl,wclzimcLi1kziuhotlS
reported to be R.celc to lisli 2. listVt'i1 ehhrurpmi il-as
concentrations tire also welt below the OS'S, n.uufi'Jmncc' lower
limit ofthc' henchunuai'k ct.tnceouluaticlum cdliii ale' iii 'nut 5tg/[.
resulting 111-2,5% bramnacetvlcholtnesterase rAChI) Inhibition
itisteellucadtrotit L2ti IiiainlUaEusconsidered astiscissiiis'e
indicat,ur of sublethal c'fiect AdditIonally, we tire lii1tt5't1c'
of an': oi'ei -reviewed reports linking lesser conrenloali inS
it chiiirpvtilos to skeletal deforitiltiec in fish,
.lE'utds tiioavaulahle heave insital satupleut were collected
using diffusive gel thin fIlms )D(Sl'j, iund samples were
depltuvcui lii lit-' sztiuie' i,ttsnneras ii coiher PSU5, iiloavailtuhtle
zinc, eadittri,m, lead, anti ripper were sletc'rmi-nedfor all six
s,iiflp ling events, liar. c,utliuufutn, le,wi , copper, aiud ztrsetlic
111 Otis' de'ic'rtniiurd iii littet cii gt-,uh Stahl samples pulled
duiltig tIn' 21111', stniplatg dc'phiuvin i'tmls. 'fhc' iuiu ',t'u',iilthic
metal u: ncc-utt,ttiuuit. 'acre - ti tht- mist pert, hs'heos'dctectton
timus 'flue univ exceptions tieR' delectiuc tI, lliuutg.-'l. i
Zn in a sIiupin suutiltle traitt Ni'wbt'rg and 7 0("l. ii lIt lit a
siiglt'"aitiplt'tl,ittt I ii''.ilhiS. Nt-itlut'riltIiL'st-dc-it'i'tlotusmst'ue
rcpli'tirtl. zini till u'ilucrsaisihiht's Ii an I' iti stit' wire li'lrutc
detection hitnitc.suu built delicti 'ncwt're ronsirtc'ied ;urufiacls,
The i esults prts'idesh no evitleiucc that hioavuul able heave
musetals 5'S'te'',i likely e,imts;' Itt the difference' tim rlelitrtttitv
ioztds at the I sea sizes
%I,itcrnal Traiusfs'i' sif POPS. (:rmcenlrat-tono of POPs
detected in Wi 111111 mcI Ic iluvet northern itlkentitatmow ovary!
oocete tissue wi-re rm'lamtvely loss', ('huitritialed peslicitle
concentraul sits 'Crept' tii'rahlv '-3,3 rtgg wet wt, amtml ml" It
of the 21 dtlfc'rtmmi eliltrittal,'mt pesticide residues aittmlvi.t'd
vine detrcicd )'i1mble St. I if lie three, 1, 1'-! 1110, was uht'iuzctert
with [lii' gi retest ii cqut'ncvand al the' gretttest cone't'tnratil ins
i'l'ahle :1. lttuttritt tund -tI -DOt) were detected in 2 of 10
sanupleszuiaisved, bath ft 'nt Aetchergff sh. l2xpn_suie 10 Partspe'r-i.tihhiun e oimmiiiraiions of toxic chiot-Ittated pesticides
similar iuu tb -,': ic tried hi the u''arv/ors.'vle ussue Irma
ci site eul the fish ztijal'ed have been slinsen ic ca-use adverse
eliu'et's in ratly lilt' stop'. tIs1 159ill).') huts, stone potential
I' ur tl.uxic effects''! ,ualernttllv trttmtsiened chulirinated pesticides was pmivtble, although tutu-re c'lornstve sttldV wttuld
be needed to tl,'tt'rimtine how probable such t'itemt arc,
Ctuucente,ulii,,i a of in,tlerniliy traemshc'rred ['tIlls iktccti'd
in uruithuern luike'ittimuuii1' tc,tr''.00l,'"te samples wt'rt' Just
altirniing. .1 tile! il ccviii ditls'rt'iit t'Cfl cuangeners wt-'re
ileincted lit 'lilt' Ii ittttm .1 the ututtpk's i'l'tthle It. t'cbt 133
scos di't:ctt'Lt tire ni.'st lr-eitueltli' u/tIl stinpiesu anti at ti-ic
grr..ttestc'ncc.lttrzstivats. uup toll 2tsg/g;'t'alhe .5, POts 00,
liii. attd 1:111 sect-c mcli deter-ted 1mm it single Ncwberg tIshi,
143
All P(J3 C Itiflc1s detected
crc mono- or rfirtim-
eongntneus ttungei loin I! .5 INSt Rut u to till IPUII lit.. In
suhsLituied.]iic.c .oiigC?fls'rS tciicl to tie I tichic, inNIc than
utiortho Imat PURs , 02.
i!sfi. 0 pat icuhtr, ha e
2003, otul;- 2 elope-nets. Ii TI) 11.11 arid itS! liii were detectcd
pc:n 101 was braid itt tin I T,:rviihs siittpie and two Xeherg
samples at eniutcentrath 515 ruinging fri un (1.3! ti: 1 .2 ngtg.
that coaxpo It C Li) the chit! rele L1lIilI.ilitC mi to- iid dii. irtho
PCB congetlets 111,0 reduce the vomit uplak.
the nun
tOxjc
isoitho pianutr lUlls
Mean c1ncsntratuoits 01
PCBs ft and ILL wre greater iii iili ciilecteul fr in Ciitvallic
Samples Wete lint Cit Ilecteil at identical cot inns mcli re-it
to it Vt-IS lit pissihie Ii thin-rut i un wheu her difleretices In
the nongetters dc tectenl is etc the i n-tilt if spill liti iii tenuporal
duffetences. liy i all. ne 1 esults dirt Oil provide ctutnpeilitig
support fi-ir 11w bv thets thaiclili 5 liii- .1 pesttn-i nbc residues
or PCI! piosetul insunilcial sill iflettts ni-ic alikclv cantse for
the grill ci skeletal defcumnitty lead itt eewherg 11th.
Skeleimul I)itii iiiRle IIioassuiy I: lOver Waler Extracts.
been shown t be less s(ritice Li the tiliflri-crthi ii:its
than ntamnii k .r hlrct i..t I. Ii lOts evrn beeii ciiggcswd
than from Ncwkrg luhic :t, (:ttver'i tic maul cliicnrnration .1 LULl I
LII iiVuLrV/(.lic1e tLswie Was gimlet in
Nesehsrgiisii Liable ti. liowov-r, teitherofihiscdiLicuritcn
Wils stgnitiraiut. t)L) Lb
basis 01 the samples an.iivzed.
niaternal transit if Ptt- di es no! ppear to pose ii high ri.k
of ovn'rl early uk stage toxKitv In \Vullamctio Rh em northern
pilwtuttiuiiue;.
PCDDs and PUflis wile detortabie in all ovarvu tom!
samples. Specific cuinginers viricd -uinsiderabiv ining
samples: then fore. a iiiiic C& uiikiiis zLpptslach !i
used to facilitate atitibsis if tiLe resu Is md coniporis iii
anacangsltesTuai2.3,7ut-TUL.)D IquivIulunis in &ICVICIIVOLV
Ususun ofWilmatncttt River nuurtliern p keminnitw ringed [rim
Odif Lu 206 pg/g wet wI Th greatest ItQ colt. titrate JI
12.06 pgfg wit wit isis detected to a fish front It lllst
PCI-I ItO it i p p wi s detected no siitgin- Os ii lii t.ilL1ii)
Results of lahtuatorv exposure of fathead minnows to
\\illatnette Ititer tealir extracts freuni d 2 1 il 6 post-hitilcit
v ith suhseqtient prune_rut to ii 213-30 post-hatch did not
p r;vtie evidetie' that utnkiaunna contpciunds it interactions
lttwcen rio t it L alt present in th p report-il extritcis ware
ltkeiy caitses til grtaler drifornilve lead:; .iluseivct-3 lit lish horn
rEam regi nt. ut the Willutniette thvir, Sliriviil
postit. itch tanged Iron (13 tnt 100% iti all trials and there lucre no
stgttiiicalii dtllcnne:es anmuingtrn-nutnacnts p. 0.2112li.73-Li
inutiealillgih;tt exiractss ri. uOit aruteit I-x.ictsiarvaifutthead
tntttiln's. SUtilVill nlcititip Pt- ce-rut was variable among
luaostvet. tiiiiitarmiiiQ roncentnatiitisweicnearlv identical
brush collected friumihe two stud" ties It.) itt r)21 Icrils
nepi mutes aiiul aliting in alt.. t alging fri ni 5 to 113 IF-h per
replicate tI T--i3;,i - itt till COsOS, ii LiLt ii ittim of 20 fish per
{L85f.0.31 pgfgwetwtfturNewherguindcoivaulis,t
lable :o Total concenirall ens ofT I :Qs wet e less that di
expectnilcijuse Li xicitvdurlttgearlv liE snugedevel ipttw iii.
Oil the basis ifjne,istiitd iiI)i) crmuceiiti,iuh its in fisii eggs.
treitittient pit-nip s-crc examined for deformIties, it wits not
pisslbie 1.1 detentniiue whether fIsh that cIted during grutwriot Crete defortuied. Nonetheless, the itick if a ugmuficant
truttui-it-ri'l;uted effect I in sttrvivuti id tie ettiliLiliaiitl day
iuilih suggests tltttt mIte inirmalit tliiriuig giveLII tilt. raitdu,muui; ilistrilt.lut'l lolling ieplin-ttcs all diul not
the lowest hserred it-fled connetitratiuti tot sewn itifferen
fish sJscies ranged t tan 271)1021 ) pg. gaset vet tu XCI
were - 175 iag(gwei vet teSt. The3 EQ coneentiatlrtns deteeted
in this studi-were at lest 135 tunes I ret than the LIEU lulv
the 111051 sen sOlve if ilit sewn species tested li'3. I-n thin morta.thcThocnn ntrettinsiteiceted ore ,itleast25 Omits
less than the prohribk iou-i iiiserva Ii lit-oil eruut-effeu t level
INOARI3 ofTt-Xs fir lake In nit. irlitch is nudely ic-parried as
the flush species most sensitive lii ditirin tittil dioxin-like
toxicity (CS CS! Thus ci.unceritrtiti nt. if nut ttriiallv ironsferreni PUI3Di, mind PCI *s dii not appian hI-tic hi eatisi rarl
life stage mortality
obscure -a tremiunent eIfe'cL.
When stOIc Ic- drirstiH Colt iruii cttrv,l(Urc CCitt. ineludittil as
a deli irini IC.......25'' ot the- Lislt etut nliLled were citissitted utt
deluirtard - aitiiuutglt Ill ti -urtetlt-llependt'tut ellect teas
ti:)
oItsenvcul i.
tiii'iui \Vlwti liii tUitliV'ils isis restricted
to nih- tb -se stelnritliiies -lior,s-leitaud as qii;titlativeit'
slmiiar ii' thrist----F-served itt Wiltutittette River htsh ;tts pr
I
ca-tegoilus uiefimmed
F-
i tIutningliant et ti. 2001 I Xiii, the
it [ruin i.1.i3';-2t for the entire
itit-irlence of de-toritti ties
pcupulattott survered iii c-.inI tuuai, Civen Ic_still sample st'es
On the basis cut the llter.tuurit, it tout. uitrletur wile Uter attv
of the couwlittationo --f Pt )Ps ileite ted in VLiitaiimette Itiver
nif 210-3137 fish pit inlal. ils represt'nteui 2-8 fish, In ulli
nartiicnipikentiiimii iiivaruiiiivie tissue wuihIle likely ii
n-I as-si vial! ii witlt lily psttictil.ir treattlinuul suit esitient_
The u1istnihttte ti ii dctvlu:ipiticitlol seuirrwls titlaffected
catusi'skniettl ii [rurittttii's. it vet-sir. miiisigtliIieiutt ii liii utters
lnmaieinailvtiuutsfenred POPeiitsemtit.0 otis usi:te.ibserse.l
rases, deformities inn-re sprr.tci ulern:ss ireaittieLtts, such that
Even 11 early life stage eapistite I 11 tlsveis cattt.i tip soiiue
mi55O,t3tij
httm-t.ituuentttttiin-NI0(T'attul.tC,ttLoi'-.
with titost fish ltadtig detelipitteittil u ures pleater tItanS.
in them ml ;\tikd. fidu trim tile Itt :giuuip terre slgiutficintlt'
disruption OfCiUi devcluipiiietit, kihimtg Lit skeleiai ulrturinu-
moie tieveliped 111am) those Inont all u titer rreatnlellt greuups
for fish
front the Newberg veisits Ctea!Iis sites il,ilk
lies, ii was unlikely to leciltit on 3--.-----ilil gr-ilct roies of
skeletal deforinitit .-\-, a. v-hole thin-s.: ut-nut. iu tided nut
mtnplhiig eviditce Li sitppinni tite- hpiititcsis lit at greater
maternal truinsler ut It Ii 5 0 ,as.i Ii kiilv e.ttise ii the gre .i ten
incidcnce of skcletii dcftrnlitii- III tishi irttutl die \eueiietg
region of the Wiliancnitte River
Sedluwut POPCAsmailuutniher CL Spot Site per ear)
of suiThdal sediment satuupies nuetliecteiti finn Newberg and
Corvallis tites were analyzed for persistent chlorinated
pesticide reshities wiui it ;Us to deuermutie whit iii tropism
transfer of these comp.iunds 0 in sediment, or direct
exposure of vnibrii-lauu I tish i tauitculativ fin lii outcast
uspawnirs; ! tOil could ItcelItIt fur tliifereutces lit detiurutittes
at the iwo sites. Chili initiated pesti ewtnt. suet 1101 detected itt
sanipies collected firm i ucitullis on \ewhcig itt either au 2
nr2uti3. 1ii2002 Putt-ti wasdetucted iii a;:I t:ireailissanipies
and t Ut Newberg tuiuuiple. t%.iticeittrali,ns it too it i-it-irul
ijuan 13 LI) 66 ng/g Addtttitna.11v. PCI! i2tlaas iliieiicut iii
a single Corvallis sample and PUtt. Lit. 101 . utuid I hi:; Wilt
detected in a single Newbergsunpie, Conceiiiraui ui if tiusi
0,02-li, tI,------en, Ill cttiiceiitratiimi-ulepeitulenre nuts
evident. As a whi ii-, there was mit t'tl deuce that Willainrtie
i1
hirer Isuiter cxl racts lilduiceul skt'ietah duefc.tiiti U-stir odterselse
adversely Iliiietu'nt latvil lillietId mttittncuws t'N)uuistll fur Itt! h
from d 2 Ii, di! lli)st_li.uln 1,
It flutist be it uuteul, hu;u ever, that a tlC:Sittii-e I espotise In
the skeietil delontuties Iuiuuassuiv lid tilt rule out thit
pit.sibilitv limit chcitiicals ctjtttai.iied tnt the exinlcts had ihe
pitritlil tiilinlildl' ulehirtittlicttncvpruttiii tiiit.Asdt'sigtted,
the assay itis stile tm pm uside ut I (its ti able cci ct-ti fir the
p itritim,iI it the riser iu'aiet exliaei ti disrupt ii ow early lifesttugl' ttevr-l'ptnnitill pt-ici't.sl't. iittuiirtatlt lit lurin,tihuil of
the u'ssllii iii cituhual cilutnti tin assay Slims lltit uOipn'cted
to be iii elleet lit' sun cr11 fur cllni mcii'. tide tn ctmlise sI-el etai
U. fuirini mies through acute- tlellrtinsttscui;lr damage, A timesin s-s Ii ir skelu iii
tlu put i'nl in Iii \t lucid unnlei ass a"
umoliti itS sh,wttl that ,is ,-arl it, ii 5 Ilost-hatch, nearly all
fish litid ossified sI.ulk-,ittd Initial teridural fonttialI-.ni, as
lnthcttte-d b tassilyttt run it iOn aultenzr)r-n)eist centra fun-
published resuliti .Atteutpts to validate the assay using Cd.
or, is, NO. 10. Loom Et'ivIRONMEtIT.SLOCIENCE &TECHNOLOCY. 3503
144
So, and ehloipyrifns as positive controls s'cre unoiecessfuL
as dckrinitiL's ro not Induced atnonlisle )nicIltt011005
hmlltbhslwd results). Robust application ol hi mviii Idseill
require additional characterization cit th LIcILcILIbLO niLelianhsJn cit acron and further oplimizition to ridmin' Irtality-related vain h div during grow-out.
Ac,cIatia oi ParNtes with I iIinhitie'. in kid
QIIiX.(d lisli, The imcclivflrv f keleto1 d1-lonuiliis In
Wllarnelte urn fish was siroiigl lii k1'd with uci.occl cailac
of a digonetin treuiatnde, likely oidiflii.s d iii0i (317, 17
4Anirnalvsisufciriirrd end smaincd S1L5lillhmlsrf ii' 'nhins
ptkemlnntw; and rlttii'lni nOli c,illcclvd trio (Lii Wilbinielti
River locattoits. including \ vilmeig. Wtiwitkmi'J kily and
(,orvaflls [7gnre I. rr,mjcltisjed that Ilic' probahilimv .1 having
a precaudal skeletal drkrmfty was strongly dependent on
the number nt trercatodi cySts in ihe lush 'p mIs iii and
the location in tlm river Ii
0 (100 01. ipecirL. and fib size
weremit sigltllicani pri'dmctoi s I 111u1 I nn,iti.des were dirctiv
assiclaLed vith tilS.5. iiil2 pFirll.ur picull irtuimmuts
dCll.LLted iii ehlscliu,iith and t7.:C inortimeri pileinintiw
(it
323. Add.IumnalI\
a 1 Ii viohis sp., Orb
cvp,iei was issu.iited with a sigiticani pvcrc:nt 7.3'..
northern pikenini iv wHim Insiilgicil!v snrifi,ihle skejetil
de1urmitie- I Ui. 'I1IL' rr.ul sIIltge'tvd hit sirisiles i;r
a likely raise tIlt the kihtil tifnrnmitivs 7 -rivi:d in
Wihlantertim Ithier lish, I luu'i'snr, sick on tile bask .l
exanainati on iulield cuillectod specimens Ii was lilt jLIlieitLlQ
to doirrinine whether piOlsi In's wele acnmalb using ii-
formlitrs ui whither dciujrrn1d fish worn' P uplv In
J
vuinciabir' LI infection skeletal I eio t mU k's [lii iIa V Ii I xpi 'n i' Ii. ti;diui[Ilis
ilsnteitsi eIarilc.Itssullsftlinl,IlL,,It,urinfeutI,umstIIIILs
cins-incinglv dentuitstr,ited unit Sri tsltt,ii ul,'Iirnmttin'. riOmiiitnt ivith uSC .,IssI'VL'I
Villani ,ttr RIver fish ru Id lw
caused tiv tieuial 'ic ceLLular idinithecl is 'L0;,5i:s
i,ea-mia (Figure 2i. F7vi' separate exposure trIals u'
conducted wS!i t1iilitd intilniws 1 L'vpililid pL:CII.S) rulgig
from ti l 23 days aid psi-hatch' Mortality was variable
and Uea hIgh Lit hu II cereriar-tapsed
i-I 17(.i art
control fish 5-ill. \i.,iinlieiu'ss. ci.,ttchisI
a', c.i&ild be
drmrwn,A high i iteidenc,' of iitlectii II 13111- lOUt] v;is hserved
in coreariie-cxpusrd tilt front all titus ,,uid tnft'cieui lisli
exhibimid a high invldei:ce 'ui veitebi it itehritmiucs ,Tmi-
Table 0. 'dust deIitiiltts weri' directly ass' ciated uc!l,h
meracercaijac' utigurs'
oIiul many ill trenillodes wnri
sure not found in the viscera. Si iii hr II) I(IO[?ihJii:l] iiv in
the pi eseul studs, .3 L,,'ds in 'el low perch .ipprcunthv LIII'S
not infect the visLim al rgoi sOT!, I ad n clii. I (3/u ,hiserit'ed
bony osm,lcles Ins-chow perch C'd hr,. iuim'd. Infections
brother nietacerca.rtae types Ii' n brett linki,:d to vcnn'brai
an nina lies, ytmm'cle tnic'ctions hi' 'bu,'i(l
as nod ,io 'ninu,s
caused vertebral defoitnt ties In cvprinld fishes ,iIuy , and
Fiilwcioce sp was suspected to be a niiilir cause it slipernuinerarv linibis and othet vertebral chaisgos seen in Norih
Anhn'rican frogs (Ti]!, Thus, ta"tli empirical e'ddence and
literature rt'imrts simpprurt lime i'neiiiion thai tremarode
parasi Is are u'ulusimig skull-Id huh 'niiiitie's In \Vlhlamette Rixvr
[LOt,
1"iittn s' linesuigauin. dud ugh pa n-intcinleclionisltkvl''
the pnmm-iimts' if skeletal defo rttiities ii \ulhtnmn'tte Ether
lishes, qucsti'Iils ri'ittattt as i tehetlie'r sp.ivai dttln'riiievs
Lire due to itaicril or illlolpugeimI f,ictoi ' icremsed
nL'curti'imL'c ii mwinatide itivc'livmms hive been iiiim'.h to
rmnmrlui:pgcnic huvllnttiiu and physical ahmerati,in ill aq SUe
Ital'itmis C1isn'li hL'u'litlin.iIl acliu'itIm's i..'. I'iIeIttiihsIin'igisn1
lmr'tti.,i'it i'spuismii
lti'rbi.'idn's amid pesticides .ini susurepmm
Lmhihiii'
I in 'gs I
niiecumn hs'ilmctulcu'run.inw it li!m't'iul n.'
unit l'i. ': 1, 'i. huts',' il', hen rep 'nird i 7,' N' imie 'ii the
chemical cnlutuiitant, dL'Imci':,( ii this study an' kuwn to
cittsc ilitmnune sllppressiit ii linreloe SIISL'i'lttihihttu to
iuficiiu lit at ilin e,unc,'iutlitl&tis uhsnr'.'m'tl. I lluwuvii , din
lii 'ligI cal assays used in this sttiuli'dl ii, it test the interaction
hut Wi''Il c'xp.silnv is Parities amid e'sprsilrs' lu' cmmtiphex
iatixtilil's ml 'li'inii.mls pit'seiit in t5'thl,itil'ti,' ttivs'r w,itn'r
svdilnvmtm t'atcicls. 'this would h a usiutul step lultuid
dr'tu'rnit iii ig it'ht m'iltcr tliu''.e ehnnit cal'. pr till 'lii U'.ci'li Li iLhIL
toplr.isn's.'\lin'lnCmltLei. uitsp'ii'.stlti that '.patialdihlu'tint't's
in detdritutlu's rellcu't Li tiattiral Illicit tfln'tlOti, th','1'ii the life
00, an:,' hiimiOt charimctens ics
cle ol,tii,ims'ihia
las's lug tithe time iimtu'i inL'didtu It' st I snils such is / i:ii
'd
IT lhedc'liiiitive lust hsh-uultttgbmrds rould
rL'sti hit gnu'uie r In mini i,.if . ahu lid iunce mind p utenU alt''
nile inlectimis N mtilriillilctuuns, iiiilau'ttrimmgllin vi.mbiltivatt
nwuhens of ttii':uuhi,ii lid iulilw Ott Its lgm'ltIs stielt as
(ill]', nun- also plavar' kAulditiuiiLIt 'nil' parasite ecohugy
ui,i potential int,'raeti,Ils suith .inthrupogc'nic' ititluences
con Id Itch dr'tu'ritalne appropriate nianagentetat actions br
al l::ted rngiinms cif the 3''ilhanleitl' lOver ilIStIl.
.i
dirL'etiv located along dii.....rit'hiral column, The types ii
deihrtnith's observed u'eie ahsi.t identical to thse i.ibsi' I'Ll
in fteid-colk'ctc'd sprcinieits 110, Ji Including 'itta sl''
ltsrdois, fused reticbruie, anti itereasid vertebral deiisitv
(Itigure 21.,"ts in hrld-Luilleele,l spectnieris. lumu'taeu'reanam
occurred direrlir appressed in or dt's'1 i';it liii vertebrae ,ntil
were often assnd aU'd with hi ilL ll''pertt03ilt\' lit cmntttst 1.1
eercarlac'-eapisedfmsh. unIv It if tilt' L'IIlIIuI ic-h CXiliilleih
exhibited skeletal dt'lornmitles Table 1!. CoWl ii delmimi tins
were characterized as riIfVatutli' i clii' spine
fused
vertebrae. The Incidence o 'duetn'tal deluintitles in LI trol
fish was similar to biiekgj aid rates of skelebil ulc'lLiruulies
determined for lab-wind latlwad minnows ,x,iiitin,d h'
ilLiclrericenee micr.scipe a'. part of cxposules I. river water
extracts.
Coutrolled lab at nv vp sure to .3 mInOr: LvplirilCd
vcrtebraldoformltiu's' lusnn'e,l iii fish eohle,'tiuliriit lIme lild
andfiirlherdemottsmritid Eliot this pirasitcwashikei a nlIJr
cause ol dn'Iortnitles H 'i:'Illwiie.tte lIlvor cvpriiid lilt. usfs
hcterph'eid digencan irvin. aIde exhibit'. broad hi spedficitv. illuu'ting mail s3i'cIes in liii Iainih 1' priniiac' Lu'.
as jOb tint sc'vii,l then tnnili,s I/Ui As iibscr','eLl in
both our labora tory and field studies. the parasite exhibits
remarkable affinity for bonn' I Ui ITu. Most of the meiuic&'rcariac were associated directly wills skeletal structures and
3504
LISONMENTAL CC!ENCE & TECHNOLOGY
'DL. 35, NO, 10, 2t05
ckn oJle1Igui1eHhS
this c ni wi's sttp[ rind i-v a groat loam the
i uregmi i
\Vaiu'rshn'd I mihaitc'eittiutmt li ard (ni 2uit -502, ,.\dlhiti,inal
suppmi'l. irs tim,' aspects nI the stud\' i 301' tdemi liv Nit] IS
L7_'ntcrGrint l,Tiu I:Si3l:Ulitlirotigimfliegnn St!!mi tJniii'rShy's
Matins' U tr.'situai,'r ttiiiunc'dictt I titer al hr diii Orngotl
Agticultiir.ti Fxperhittetit SiLitloil. specimmrns were collected
tinder Oregon sm,'ieiifihit takitig pvruliis I Itt 2002-1 15 anti
I 13703-117(3 amid aNu iA,\ Fisheries 1 d authorizationletter,
'V also thank Mark \Vilh,tIns amid l)rk' Johnson.
Supporting Inlurination Available
tm List cii all target attal is and p.iratitciers analyzed Liii part
itlnsirimmititining with .1 Vu/I ('Pill Smile umoIc andimi situ
stmnphng et hioa'railahhu' uiiinin' compmunmts nd metals
mmsimlgt"st)s mild 110 F'.. 0,0 uhiitnmimilf I] ,!-Lahle-cigc-n'Lihlc'arichot SL'tlip I:; 20112 and 2m,um:b p11 id uiIlt irentis. IIm list
of target ,malti:s aimaht'aod
its
riaryfoo'1u' tisstmi's arid
sutlaclmI sc'dinie'nts mud 11w' eindiittr'ations duin'ried in ccli
uatsmplc. iS ck'v.:'lcupnietital sconilmg ci itenii used or t'athiead
tastnn(mw skeletal dcfnuttties IS5LtV, and 61 ('iLitlTphes II
dclrrnmmties nitseryid tnt fatiaead tnttltluwskek'tLIl del irtitines
dSSOV 't hats inateilal Is available liii' of diargi'uim the Internet
at htIp (pubs aCs 0mg
145
clii t'ut(b'iurit-p.diutxitt tunxiriivin the rc'brafish enttbrvte altered
uegtruuul hi-id f1tiu atid iutp'aired bear (.uee du-wlept'uneut.
Litetature Cited
Urkh, l. A.; Wenti U. F, Biirennieiital wiling ri the
ftTflIantitte basin, Oregon. WriTer Riecureri Iii nnitgaTiorto
Ileport 97-4(123. U.S. GeohgKaI Survey; Portland, OR 1(1411.
Wentr. U. 5; Bonn. B. A; urpenuer, K. Ti; BunkO. S. H. Janet.
1.utenen,.k; Bencala,
M.L;RineJla,lr,A,;iJhrirIt. MA. Walte,1.
K. H. Walex (1uaiiT\' in the Wi ('uiuuelte (aint Oregolu 11(1)1
1(1113,
C.urcular ITRI. U.S. ('i'Ogui'aJ Survey; Pordaud, Oil 15)8.
H.; F uaeui.C. St.; \Vuul.e.I,tT. S
of rOut on
Ott aquatic biotu and their I ibilat' in the V'lluiutiette bnaiu,
PT) Altiti
Oregon. through 1(115, Waler. 8cc Litres Iuvesti(1atioos Report
97.4033 U.S. rr.'lgiral SUt'VeV. Pihtxl, OR, 1(1(17.
14) Ilenglnetcui, B. F. Stof girl I aliLittles. ci Iucclallv skehetil deferniitieaiti our tush far ni 'tti triItg it run I1l1uitiott. Phi/on. Truute,
A Soc. 1.ojok, _tJ 9711. 2Sf;, ii?
(5) Valentine, U. IL.; S iii,. ST..iiut ii lIner. P......ninetry aunulvaun
itufishes; rt1ieu.ublrsl,ttusrk'al ituulii';i
leiinrottmetttalatr''ss.
flJt Ruth \ iii
(lIT Ln'nily.A, r3..Aiet'ai.fn:lll(.:.vrnd..o lol'(".'.ilui:ititl(1ilt)ntc
ofieleuntiuu out fish pcnpuulnui;' L,to.v2ti. F in.....'
37. 2(15-21181.
ulics in fish fr ii f3llutad urfiurewuters.
Aqtaail ToxirnL I51 21. 57
tnoTcu:uli,' baue,f ruittitiuuna-itttltured u'li'lu Iitiiii'c lit zu'htraflsh
c,ntbrivuo. LoCrrar Thu/wi, Ot,',it. 211(51, 19,:tb'tli '.1)3 I
2(1)1,
261 lleauuuiult, H. ). Lethal p1'1 fr Ihe wlti 5' si.n.f.t:r is;'uttus,'tntnue
1172, liSt,
'OCt51 cr10/il) iscapedl. . 5; ia .4ieu....';
(macside, H. T.Sciuie t-th'u:ts cii rcvgt'ul in nu-luihotu In' tetitperatLuTe
'f lkt' trait titbu'u' 5. (il/I /eui/. 1)51), .57,
11ii1iS0.
Abdu'rdice, I). I . IVickeit. VP 11; Brett, 1. It. Seine effects of
ott des-elupotett I
1211)
ieuttjennarv .au(u' cuuuu' ti Icier dissolved oxygent levels en Pacifiur
su)na',tu eggs. / !'utb. II's, Staaa'd Coat. 19511. .15, 229-2411.
Cahtriel, St. L. t',t,'iuts .uffa'titugtlta'niti'nber and Bnit iii vertebrae
i301
itt .Futnduti:ta );u1t't'ia,' 11/5, 1. t'.' Zn .I '1.14, .1, 1113- t33
Ks,,aiti, IL'. F.tnbr'uuc ik'us'llnuuetil, u';irh'(1ross.ih,utuuul ittenistir
II) Tibia, until an investigel kit if pliulbIe unities. I P08 .ihIu/.
73
/17) Muore.C. 1.; liBscuut, LB. luucideitt'e 'if rab (venl.Itril cctlnnuzis
itt adult Pitnt'um tiiverwhitc'perr.h, Mntnaute-Atni'nicana. Pej.'cB
1977,2,
i.l3S7.
r iuibu'a intuIt SOlute gutitcifii'3 exposed to
rtauuthiuu;ti, 'nc) light uuutettsitv and trntperntulre. 1. IS/i. .Rn.
variatiott in
I
(B) Bautnaut, P. C.; Bane tent. S. J. Sen uhral abnornirili lies iii white
crappies. P noun ,'tetaiiti;i 1.liPc''itj:ie. froze (the Deuratir
clietug.5 lb.; UsiA. If. ITs So, Cli.; Wit, Ii. S. S. cellular and
25) I'to(itar, 1. 11. tig ;uitatl Iat'valsutreivuu) ofwltilu'stt'kt"us iCun.otrIeLtus
contaucraouri at liter pIT. I. F/alt. Rca. Suxirn/ Luau, 11177, .34, 2k2-
I
I
(7i S1oot VP Skelu'tuI nut
Tta'i'uu/. 'i'm '2111)1, IrS, 1112....150.
12-1
33tttri( I -'s. 11177.....- ;'.'t7 402.
Si) FlaIr-n.). I.....-5.lf.':. L. St.; Snnith,t(. i),3scitrbic add requirentenis
1 nr.hui e.tluu. 'I .inI t;uuttbiwlrctut_ Traut.u.,-t,ei. F/sb. Soc. 196(1,
P21 Kl'pl;l'l, '8. \l.;Post, C;. l'Tislologic-al ali'rstiotts itt trvprnpltait_
d','In-i.;'rt ra;ubesc' trout, /, ,SSulr. 1075. Ic'S, Ii;)"
lletlgtsciuti, A. Effe.cisof bleanlucol pulp null efu'luettt sti vertebral
clnferla In touritoru 'tulpiu 3! nruru)liiul!:us 1.iiii1r.vt'O1s t.5 hi
thi CLIII of Rotluuia,Ardu. F!wlr,.11iioj. 1.11, 121. '3 'at.
15':; Stt'Kn'. C H,; ClIerde. 11. Gene-tie vari;u I'ti C,..,t ci,o nil di'fc't'iuity
I.lndnuifd, 5.; Titutlitu. I. A skeletal deknr.tiice if r triln'rit pikes
(Eno.r (urine re!aued to a:' lutz))
ai;s. 0',;. 1. 1 aIr .4u ui;.
34) P;tuivton, S. IT. Venir-brail colamtt tbnttnttnalili,''. itt brown Irolti,
Sruhitio tr;ttnt t.. 1. 1';.slt (lie. 1957, 1(1. 33--ST.
125) Priori, 5.0, 111,ouiiauueoiisskuletaldniionttuitirisitu thezebradank'
li?ra.:i: 'Stir's., icr/i tic-..) fi.tr fish tcunicitv test. I, 1-SOt, B/of ISIS,
13. 71 ;;3.
361 Kutul.M. 1,.;) a..ft 1.81.; St'uicu;n, I, K,; Yasutake.W, 3'.; tOlL
A. Spinal as-.; In in lug ttelt;ivt.ai titue to cranial otid erriebtul
lesions niasectateul t'.'i: It C.'e'Ol)ileiiB/ 1.'o;','l.'eu1tb//a infectious in
sahiticinid fishes. D.0......('alt! (5,5 hIltS 15. 113-121,
137) L-ipatra.S.ti.;BsLa. 85. N,; ItIL'rlia'l. K.;J.aiies.t: H.;Shiewtnaker,
IAS 17.; Wiittott. 1. Ii. Nu'g)igihtli' risk ssse'iatc'd Is1 ththenioveiuent
of prude-ic I in i;:t',us' ti' ut, (.a.""'tlIi't.! 'ii tue uri'kiss lWalbtutuni
.ca. is'pi. 4s. in
112) Ellis. S.C. 1.
uI
wutrul,' .qvt'st0'L/ihttien h,'
Ilit,sn'llnao. 1','j.o"t 1.rti;,'l )nt),ol' fa';niflit'fi( I. I'''
t15.t1511' ,'(iluI;i,. l., trt 's l:et.'u.'
No. 2/53(1-03. P1'b, ti, 2ftiitt. lithe. lWWiC.dt').5uiite.
51!latttenti'.seqsl itdiei.e.11lrn.hskeldetonunrpt
.11.
(.131 Elba, S. C.; Deshlet, 5, I,; SEller, 1), C1aract,'nuaiuu 'Oh
aowrub]ages Jut the Wlilnuitel.te River. Orap ii. toittg three
dilfnre'ttt. bie;tsssuatent techniques Ta trh'rt,:u/uv!';'ut
until .Pe'ausrilS;; Laeute.n, A., t'luututl-ite. Iii. l.;ds.; lewis
Pubhishets: New \urk, NV; 1117,
(.141 Mnrkhe, ISP.; Prettcli. IL; Nujittan. s t:lcttuItutl, I.; Batik-Id, M.
Hislorkal piltet'tts cii okek'ta) let 'unit ti's ut 1 ii Is's firant the
WilIatnetfe Sisal', On'p ci. .Varu)uuu-N'r,: Vu:. 21)02, (13, - 14.
(15) I'Ioiconube, C. 88'.; FouuiL, P. A; Leout;trd. tiN.; Skkiun, J. .81,
Iaung-tertnuinflus't ..iif Laid ap cure out i Itru' gi'tierati ttsolhtrontk
trout fSalu'eliuttri totiitii.ul.,i. I. 1a)u 11,1 ficenu! (tilt, 19711, 33,
1054- IC/ill.
Ilk) Hudson, P. 8'.; liii. I, 5''.; Blunt, 11 1).; SInger. S. 1. lill'erus iii
dietary aserrb 'a,' it itt chronic lean t.cxu:iuv IcyliutIg tuatbuw
trout lSuino 5i1rol'ui'. OW. j. cnlu n rut c '- 1 uttIL, 37, J7)
.175.
in .8 iii ii,' sal mciii, .Suulutus ,calu u; .tij;5 o':u/:iuuu' I 51143, .30, 210-
nnI'ecui.,iis h'sL'iti;uta1tr,i'IiC ti-ntiS virus )tl'INV)
ettlenni,: ,'t cc's. I, 1./sit. Dj, 2001, 2-1.351(1 .117,1,
FIuil;'irk. it. I".; Eb.Staibonilt,M,;Adkusoit, SI. ."s.;Ma'i.ontiell,E.
Irtiuti atu
13(1)
SVluirlL rtg di cL'.isi ru-cltt ergu'nce ntnicutigwilti I 'itt. I;,'n;tieto/, Re,,
II-),. 33 '.17''
139)
,S'lntlI,''uni, I. 1..; itt-vu. A St. 8'.. 1.arts'eti, F,'.; t)ishcja'htess'aru.
K.; Rr;'rs_ 1'.; keot. 33 I.. P'iu'n,'l,'llt.ilttL un'ilm1s:;;al lug., tt.ip
a ttew gu';;iic i;iI sp','i'c'.I' .'sli'nc).'ei'itll;l Ii'ouiu Itt' u','iiiral
nn'tan,uc cycle ut of the zebn,ul'i'uh -:. (('.1 n;COI. 8. f.ui i,.\Iirnotuiol,
20111, 4(1, 23:125.5.
il/a Cntuuuiugli;iuit, 33. F.,; Mat'kle, H. P.; WaIral, V. Cs; SB/itt, 33. 0;
(17) Benglastait. 13. H.; Orion. A S rrteltr,uI ,tel't'uuulla:'s id pI-slolegiculi-t'fs'tsitu i'iiit'Ito"ls'nlpun uSt'eptt.ituusqttudriu'n.:ruilsJ
.inuuu)aieul Itc.iu's-ttte it) - couztatiittg
alterhoutg.l into e'sposuur'
'i3 Veri,'lir.tI l;uuitre3' to Itlitugills
Lii 51cC_tint (A. lisper tO..
exponed to usrnii civ t ruin luui'ku.f u-sl:rilec. 1' iu Its, Ii ii, T''.It.
Soc. 101: .3t7-322 itilerit. .'tquuuui. Iuyfrit/ 19111;. Ii. 215
I
(TO) McCattn. l.A.; Jasper, iT. 1.. \'u'rirh,r;I ,Ii'.uu;uc,'. Ic bluegill,; espr.sed
to acutely toxic level. cf lut'sfi'Id'i. ;rr,,t, Sit, ls.u;i. L's'. 1:172,
lOP 317-322,
(15) Heou7) IT. IL.; Spitsbergeit. List.; tIn uatg. 53, 3!, ;.,kbit't, u:. C.;
Perercon, tI. 11. Furl)' life siege toii'ity if 2,3,7,8-I..,irai:Itkiro-
Curtis, t., B, Patterns of fish duforntltles and their association
ertult ireiuunic de cysts in ihu' SSllla tuietti' River, 0; ac;' 51, !Stt,;lruei.
3/ni, Re'lien,
1413 I'huckles, I. N.;'t'uthnrgu'ut. St.VP; fd;tntuuu"yi';t, 5. P k"nuipu-rttieablente'iabrnute dcisicu'c,'t.ititaittiit(1 ttti'.tl'l luTil 1 iirov;ub'tur'.nnh
to ttiouinaaniugtlte biu.ivLil,ubilit\'ot'ltp,upliilii'u'olti;ittun.titIs ted
estiuuiuuu:gilau'inlui'e'o ttc1'uulraiiunupot'tll LuL 1 l:tuiqtb'nt' 19013,
211 523-552,
1.12)
dibenzo_p.dinxin in ec'brtliali '15. tn 'lu/n. 1997. 1
Mehrle, P. M.; Haiutes. 'r. A; I I.nnili ut. S. I.; I.uul Ta'. 1. 1..: Slaver,
F, L.; Ribie-k. M. A. Helrtlotishtip bu.'twi'i' a hrdv tiLiinunatils
and bone developnueuut in eaat.cc,iul sit 1 Itell line. hiatt. Aor
FisT,, Soc. 19182, 111,251- 241.
Mayer, P. 1,.; Meltrle, P. 1,3.; (maTcher, P. t.. Iu;leuactiniis of
t;oxaphe.ne and vitatetun 1: lit chaitutel caiilsh. Titus. Aunt. Phil.
Soc. 1975, 107,32(1 33:3,
122) Olseon, P. H,; Westerlitud. H.; TeL. S I.; ttihlssotn, K.; Berg. A. It.;
Tvsklind,, M.; Nilsson. I,; F:rik',ts. H. 0.; llitttr,rt, U. F., liBerIa
ofiouik'nial exposure to estrogen id rs:tt rid ifl'erertt hifestages
ofzebrafish (Daub rCrau1. .'ltutlt, 1115)9, 2,1, tOt 10(1.
ii S ions nina S Okult its I
(231 1 'rioku Ii tJ,u,. 'u5, 1)
Nhiyama, iLl,; Uetio, N.; ttein'rsu.ttt. Ii.; Iturag'i. 'r. 2.3.7,8-Telra.
i-83i
It uck[tt-. I. X.; SIn tu uwto'ru. C. K,; Peter, 1. 0,; )s'Inck,'uca U.; lab',
A. t.iptd -cr.itnt;iiitittg, senuipertnu'able itte.toultrrnr.e desires Ion
inonttol lit et cii i itlantinant', In lIe-i 10 inca/i 'ti i "cleuol
1993,27. 2150... lIST..
Seibtajlt;Iaruu, I.).; ltllltcs.ilt, l..; Loper, B,; Anderson, IT. A.
Ilivarnuu;r; Hui 'it ''-It 'ic-I chettitcal conuiatttlnuttto iniishufrotu
th5' Ililhuitt,,tt,, ibsen. l',t'ti,izud I tin'S.;, (Sign. At'di, Eutuin'n,
HaitI:. i,eu'o'uP 2l)'t. 'U-. 114''' 133,
i4't) Zhu,It;g. 11.; '}i',')-iun,S',' Pu't'I',t'tttsn di' rhuiStdlu-nisticsnfulitfuisitun
gradiciitts in tltitu fins t;r tlte li-situ tnuOacunu'tti('ilt cii Irace
ntet,ils it: aqiter_luis siuiUtir_,it. A,si/. l.j;ult, I 5457, (7,339124117
(-13) tu'otpiui. 13. W.; Ftirlottg. E. IT.; Steve;. 33. T.; Tttutrnnstt, St. 17.:
zaugg, S. L'S,; limber, I.. II,; Biixt'tt, II. 3 Pherttuau:euiticuhs,
hcinnnotirs, and oilier organic Is'uuciu'water cclnutat'uiulnrito haLlS.
slreattts, l99CI-'2810; a nattenal r--;'tunuuuluuauui'e. Stun/mci, Sr/.
TnOt,te/, 2002, 3)1 1282 1211.
VOL. 20. NO. 10. men: ENVIRSWMENTALOC1ENCE & TECHNOLOGY. 3590
146
(4f
Do. 0.1.; iroirkol. V Kiudahul, C Zuhar, 1. iauuliarirrg iwrnral
and dc'ior'iiv hera' cieveklpuieat In zelrr l3slr ernbrrs usirr
(oUorc'so'iri 'Iii eeoc hare c cola, JAr.'. Si
2001. 236,239
246.
(47) Koru, M. L..; Wanal, \".; Whippu. C.;
assesoraerm Cim',rrnrrp.4;n'r,' 2(1113, 33 IFi, 1110020.
l'pslfti5e l't;it'.rlraarr. hltp;iiwww.pesIir'iderufrranr6i
011 )'i.535
titdex.htrrri.
urmingharn, 5'!. F; Critrienc.
C. fl. I'leklr'(. I. F.; Cur0r, L (I.; Spiledic.rp6'n, 1.; Markle', Ft.
A iligenerarr 11
iii ova nrarinmrjclrraum: jill early )jrrough juvirii1e life cvole
tricercariue i.4.n'er,';ia
'.
11121 Walker, 13. K.; Pcteis'"tr, F. F. Pateaic'rna f palyclrlaerrraled
dibr'naeip.direein . niilrerrerfuurur. and lnupl;a;rl .:nugerii'rn, rm'l,n-
rud a urywzaaa
13!orrrbohiasp.i rasor lirid iLlivrrrtebril ii i'rriiirie' in cvpriul.d
ftshern frcnu the Will burette (hirer. Oreorl. j. 'bps. ii.
21K!.!, 15. 110.. 121.
'icr. (('a Ith
Noah. LI, F: Mucy, 11, 511. 'tIm Ftc cycle arid riterielrv Ia muir
oi.hpalrediria ne cilia (Skrjalrin arid !.irr.Ii..p. Ii) IE''ut'roirir.
EE.nl3,
1'ln'tOrofil.,ldaci II (1I'ii9eilt. PT'rr'rI, if.'.c:;rl,'ae......
14'ijrl, 1974.4!, 223 2211.
(413) Dinp,erkrra. C.; IJirier. 1.. It. Errzi'rrrccIcarirr üfrli.ur biLls qiltmnri
whale rrmaii r'erlelreara'. Cr danio.rnatrariarr rat carthirga. strain
t'r 2.3,7,11-'.
b)plme.rrr'I r'nmp'rrerrin.rsnvinlnrm earivitle 5109C mi,rorl'ilitv in iiilirbrtw
trout '1 i,;'miri;e,,'r'inrsc nrikias).Arfninnt Tcnaiccni. 1993. 31. 315
01) tart 'deem limp. SI,: 0ii'jrbnemj'n, I..;' Bnjsveld, Jm,'l'.,' l3nmrralroru, Ii.;
Ci',)m, P ; t:r.I.m' lnl.; 1'.inav. 1. 6; !'tarrberg, 1..; Hensirguwu. F
'131)
Potihoff, 1'. (lear rr
Kerr rich', a)',',; )irnbtjk, r.; Larrunart, 1. C.: v'.nmr Len"uweim, F'. N
I
Lrerrr in K 5 11
ii ' ti It I P at limo r I S 1 S
Scloreuk,, Ft.; '1111119, Ft.; ')'rskiind. St.; YrittrneC. 13.'. VCrerrt, 1'
r aluiirg toclrniquev lii C Lii
(t.Lt9 ,lec:n,'m13cnr4 cites Spec. Pabi. Ne. I Ar Irimici ii Sr 'ii V
''1 !clrthvli,varmd Iin"rlrcIll4',-Slor. It. 12.. Cd.; 'thur l'reec.
mn
1
Zarhurr'ncnkr, T. Tnaxii' crqiiivalermcv fuelers ,i'!3s; fir Pnl!ls.
Pn:tIDe, Pt tIFi fur ituuri;nmrr, trod wildlife. 1:'rr'rrnu. 11r'rltn
t,awreimct', 13, 1311. '119: 'p
:_.p It. SI. V'rr'brri
fl (' ;
all r.',ririairjir's jr s,,'kcy;'. 'juL.
and cit_ia 'alumir. truer. 'tn:. Pr);....... 1910, 121, 751 770.
Ea!omo/n, LI.. ('Jn'sr''ri, I.. S. Crcen)rcr9. .5. 0.. Fda. 9renn;n/nrnt
Perspc'CL (9911, JOG. 775
r:.rlianparamive Ioieiry cl '.;F2'.il.ir'tr..,n'Iric'r.irlihemmzo.p_dicroimi (a
sevL'rr frmnlr',vmtarlish '.pm''lr; m'Iurimmg orj'Ivlile' .a,nr developtrrea).
mIth\ nan:iainua, cSriunaeicjrl fl',tr'r l'\'orkri
aumocili' In, .ini] Waler' Crrvirnrrrrlerrt Fedcrn!iaim: IV'rchingiurl.
I
Ft. C., J':'15; Snrii,.i 21111).
Incamrdona, J. P.; C liner T, K.; ScboIz, N, F. Def'r'a rn c.rrdiac
furictutu prem'.nin' n;a'u-pinahrigv ahminrr'uulrne'a in air n'rrrbryra
nrxpon.odlo pcnivcviir: iroirmalic hvnirecur'burra. Jan'.. "/'Vi' /'lnr ni.
2004, 195, lOt.
132.
1131 Eirrrica, El. F., Spn'bae. ii. I..; Fbolcowb, C. ; .. Johns' tm, 14. 11.;
t'm'rma;nrndr'z, 3, Ft.; Ericksair , ii. 1.; l'isLge. 3. Ia; iook, P. IC.
.\Jn'i!mrrn!t Jon 11:,' l,L',rnn;nnn,n;unr,rnf ll'crO'r url L1)nrn';r'nr:c'. lilir
rrmt;Jmrmiem'icarr ISiErimo
ti',ciilnt .)h.'ia.-p.lu,;iii "ii' J)r.nriLrcIm)9 anile
Ii Fr''t.ige ru's tn; ta hr er lab 'c,' rica I i(nenr'nar'iri'mnn'Irro i,;n4Sni,
'l'rma'iarL. (991, 21, 2)0233,
1631 labeL 1;. '.1'.; Cauk, I' SI,; Pn'lv,rcjmm, F. P. 'lathe eJirlr;iln'iln'v
fa:im'.rnol p tvchrIarilla lad drlreuzer.p.diaxirr dilrerrerafurari, and
.tejun,'ri.
!rrrMrn:n,n. l'na,n'in'nri thins'. 1)11111. 17n3i, .173
.51;
liii Cunk,t'.M.; ti.rrbbirrn.l. A,; EmtLIrcaiI, Ft. I"n..thdpca.K.PnaGuarrey.
P. IN; Walker, 13. K,: libel, 11.10; i'n'lersn nfl, Il. 1). Elfecisofarvi
Irvdrncarbrar recn'pr'at .nrteii,ni ed n'uela'iitc singe nariril omr luke
Oct11 popLiI;ntiauts rim Ink,' m,niirLrj,m ijir) rg rIm' 2tith I'r'nrnrnry.
Eor,'e'n,n;, ('1. 'I'ncl.'n.'s'I.
2111,1:1. .17,
11.5. hnvirurrrrriyrn I.rl I 'FOrm' (Intl ta 'I rev 5:rlLmnn.nj'nmn.nL,vjncfaf
107,1 Pika, .5. 15'.: Eta. St. 1). 'Ph' learn' rc'r.Jn:nt'.e nI' 931w çnercin.
Wuier Enrn/n/r m rnr'j'inn.(,'ernva'an,'. EPA 122-Z-'i'i.rliJl
Mjm'er, F. F. 1.; l,1hli'riia'k. 51. It. :'nlinnl urn! i.! era I' :.x.'rcnrr"
!anrer;mrm'tnili,'n,r i,'i;il ,la;nnlmran' it' .1111 ,'/:rarrinn nOn trim! in. rpia'r'a of
Jn'n'nnn JJmn:''na'm'inn .tfi,,'i;m;/ ia irrlecii 'Lit WI Ill ire' tnrel,mrerr'.mrirt
''Vol m,I,'lm'9nitnn?uji l,r'r'mqi flntirau, 'ill. i":'n,''nnai1 0r'n' (9101,
fritn)mm.elmm'rcrrmimnnrb'. )in'.''nnrrui Puirli-;rnimm
iii. GO; 1.1_S. I.lipart.
''1
(00,1 Tavlrr,I..!i.;l)ntI,.11. K,;tmlivaki' 'I' ;5.ime.I K i:';'.'p;r''ssicic..
i,,'lcta;n,'d ''lii; rrneracnn'nc',ir'1;jm'c'l'.-10,m,4,'bmnllnnni,'ri'r'iu I tt'r'irnIrdal
rmme'rmt of the Iii),....nat-, Flair arid 5'. i].dIrl'e' Sn'vies 5t'aahirrgtu'ir.
ijiye!i'.t:'p.'rr'h, 1;.n'."a/JrrEa'.'mr2 l''i,',isln'ii dn'velcpmrreitn and
DC. 113116.
in)r'LLLIir'rU. ii iii bartn: amid rlrn'itrdrnnid 1' .'u' ,'Intcrn, flit: iris.!, I 'Cl I,
1011. 2)1'' H
(513) Georgitcukia. F.; KIrnrr, tnt A. P.). i'nxin'itvn,iltlre pbutisinrtreri1t
cyelodiemne imrs,vrirides la fresImwrirer ;rnirraai. C A. 11th!
Swc'e'r.4mutd. Sn;L Soc. 1!, 1971. 233. 120
31.
(57) Citrus'. 1. P.; Soioruonr, K. IF; Finals, 1. F.; Drort, K'. P.: r..i.:idLmmn.
I. IC.; Ketiagu., to. to. ChlorpSTiten; ecriogi lii risk an',m'si a 'iii in
Niarl'hhurerirsmen aquatic encirommracrri 101: l:it,'inii. r:,orrnnn,r,
Tuxir&, 1' ..0. 160, 1"
1 29.
(SlIt Sammdahj. 3, F.; Jrnktua, 1. 1. Pacrfnc Ce,ICULerd :rn,;n'n,n1ri'ir'luo
i'!r'e) expomed to cirirnrpvrifns: hncinrrr,urk c'lnm:m'uir,ttt Ft
eullinateu fnrr ucctv]cltoiirrenteruse itihiLiirietr. Fm:n'Lnannr 'ía:
Chew, '2002,21, 2.1.32 2.150.
(59) Harris, C. I..: Sir c,rb''. '1'. 1,.,; sl'rcali'', 1", 1).; Hur'stis, .5. 5'.
ltm':ubm'vmtnjXjn'iIt- at 'x;r,'jcrn lOin like Oiti,'tr'ir r,nirmbcrw trout
(L9rn'or)nv,rn'L'mna nrrn'i'/ari I.'. i.:ipmin
i nrr:d.rk;n
inlOr
ltutrr'o, B. l'rtlrialngicab. c1rungc in m'vprurrLnt (i'' irrI't'ctn'd be
B:ncn'phrri;ia /na fsmencrrp)trna 1h'nm'r, 11127 mid 0) ,'n;r'n'N iii,' ml
i'ZIr'glnt. I traCt nhr'inr:errarianrr (l'remrrniod;n, Brmcn'pnImilidim'i..'lcini
t9nti, 27, 24t -24G.
jmk to parasites grows srroergcr. .t'rc'rt.'n' ('199, 24.
itni'La,'Z,n.1 151.'.
Till Kirai'r,
I. I
2(5!
'7) n
Lij'nhurrs. V.;Llhaaarr.s,C, Srraiiciartb'cnis("rIrl;''H'oe rer'irt.rti,rrof
,,,'liiai':'a LctI;msiS trstrlsLml'tssic'nni. Pm'nn'ciailo!. Trndnny IlIrlir, 413 3 17.
73!
Kit'i.''k,i'r,
1.
.13. svmrergoettm betweirrt n'irmtn;nmade ijrk''micrii arm]
m'stLcinCm'xpauei': Slink to arrrphi ni nil ilr'li,j'jrrmlrn's in rralure,
lOan' torn;! ,knc( Sn'; USA. 2(102, 11.9, 0000 9004.
irio.'.'rs Inrarnn'r).
.tirrtcrear. 'l'nnancol. r trait, I I Pr, I'i°'i I lint
(00) Viltalobus, S. A,; Papeanilias. Ft. SI ; Parer. S In,', ti.Ianikertship.
A. F.; Meadows, 0; Tilti 11. 11. F.; I icr, I. F, 'tOxic lv 01' o,)1.lSDhi
to mmrdakam d.rI( strain after n rim".. Mine enimhrrnrr;n' rrpsiiru' b
3OEn. ENVIRON?.IEt.ITa,L SCIENCE & IECHNOLOGe VOL. 35 N'). 10, 200E
0n''iista(inlu' ,'';';,';l Sn'ltC'nr:inr'i' 1,), 21,1,1), ,E.a'i.cm'n'! n/Lnu;l.ec'i'rJ)l
.1i.rrn3r 11. 21)12 Ac'c'i'tn'i/.5U,i'!i 17, 2ofkS.
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